AGC Book 20% Cyan Karl Fischer Titration

GTP Brochure

Good Titration Practice™ in Karl Fischer Titration

EDITORIAL

Dear Reader METTLER TOLEDO has an excellent knowledge in any kind of moisture and water content determination from % to ppm. It is of crucial importance to select the right analytical method in order to obtain reliable results that ensure quality and properties of the products in a multitude of industries. Karl Fischer titration is the method of choice for water content determination. With the new generation of METTLER TOLEDO compact volumetric and coulometric Karl Fischer Titrators V20/V30, C20/C30 and Excellence combined general and volumetric KF titrators T70 and T90, water determination has reached an unrivaled level of simplicity and security. This helps you to perform your daily tasks in the most optimal way. In this brochure a specific focus is put on how to perform the Karl Fischer titration analysis the correct way. We would like to introduce this to you as part of ‘Good Titration PracticeTM (GTP) in Karl Fischer titration. This brochure comprises detailed background information and recommendations about: • • • • • Chemistry and control of the Karl Fischer titration Practical tips and hints on sample preparation and instrument operation Measures to optimize accuracy and precision of the water determination Selection of the optimal method for water determination of your specific sample Trouble shooting recommendations if results do not coincide with the expectations

This GTP brochure in combination with the application brochure 39 should serve you as powerful tools for trouble-free water determination throughout the whole lifetime of your METTLER TOLEDO KF titrator. We wish you great success and enjoyment

Hans-Joachim Muhr Market Support Manager BA Titration

Rolf Rohner Marketing Manager BA Titration

..24 4.....................................................9 2...........................................................6 Dissolving capacity of the solvent .....................8 2...............................................................................................................METTLER TOLEDO Good Titration PracticeTM in KF Titration Contents 1 Fundamentals of the Karl Fischer titration .......................................26 4..............................................................2 Stoichiometry of the coulometric KF rection ...............2.....1 Indication ...2 Two-component KF reagent .1....8 2......1.......7 2.....................................37 4...................2 Concentration determination with di-sodium tartrate dihydrate....................................... The Karl Fischer titration..............................................3........3...........................................1..1...................20 3..............................................................................10 2...........32 4......................2..............5 Limitations for the use of the cell without diaphragm..........................................................................................4........................................18 3.............33 4..28 4..............5 1................................................4..................19 3...........................................2 Reaction rate .....................................2 End point and polarization current..........................................................................8 2......................................................................................16 3............................................2 The Karl Fischer chemical reaction ..................................................33 4....................................................1 KF coulometry .....3 Concentration determination with Water Standard 10..........2 When do you have to replace the electrolyte? .............13 3.................3...................................................................................5 Karl Fischer reagents with ethanol ....................................................................4 1....................................................9 2........26 4...............0 mg/g ........................4 Generator electrode without diaphragm ...........11 2..9 2..............................1 The influence of atmospheric humidity (drift determination) .....2 The minimum and maximum dosing rate .....................3 Volumetric KF Titration: Titrant concentration......................................................13 3...............................14 3...................3 Secure draining and filling of the titration cell: SOLVENT MANAGER......2 Coulometric KF analysis...1 Principle of bipotentiometric indication .13 3....................................2 The drift ......1 Filling the coulometric cell ...................1 An historic overview ......19 3................3.........2...................................................................1 The Control Band ..2......................3 Consequences for practical applications.....26 4..............................................1........................................................................................................................................................1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration .......6 2 Volumetric and Coulometric Karl Fischer Analyses ..................1 One-component KF reagent .....3 Iodine generation.....................................4 Control parameters in the volumetric KF titration ..............................3 The Cautious start ........35 4...........19 3............................1...................................................................6 Termination parameters for both coulometric and volumetric KF titration.............................................................................21 3.......34 4........22 3......................................36 4........................................................................2 Working with the coulometric KF instruments ..2.......2..................4 Concentration determination with pure water...............................................................12 3 Titration control and end point determination........................................1 Volumetric KF reagents.........33 4....................................................2......................2...............................4..........4 Special reagents for aldehydes and ketones.........................3 Stirring speed and dispersion of the volumetric KF titrant...................6 General recommendations .............1 Titration stand ..18 3.......................................................4 Polarization current and end point...................................39 1 ................28 4........................................................1.............4......................1..............3.......................................................................5 Cleaning the measuring electrode .4.....5 Application tips .....................29 4..5 The solvent..2.............7 2.................4 Cleaning the coulometric KF titration cell..........3 Pyridine-containing reagents ............................................................................38 5 Sampling ..........7 2.5 Control paramaters in the coulometric KF Analysis ......................29 4.........................1 How often should the concentration be determined?.4.........................................11 2................4 1........................16 3.........3.................................................................21 3...................................................27 4...............................6.....................................2......1..................................

........................................................................................................6 References............4 Sample preparation and input ....................................................................................................................................45 7 Release of water from the sample .........................4 Technical products .........................................................1 Internal extraction .......4............................................81 11.................................................6 Food ..............3.........67 8...............................3 External dissolution ..................................................77 11..................................................................79 11..................................2.........49 7..............77 11.....................................................................................................................39 5....2 Side reactions ..................................90 2 ....48 7................78 11.........87 11.........................................................62 8 Measurement results ...........................................1.............................................................60 7..1 Liquid samples ......................3 Reaction with iodine .............................................................................................70 9.......................4.............................................................................................................................................................................................................58 7...........................................................................................................................................................................................................78 11...............86 11............................................43 6................................inorganic .........88 11......................................86 11.......68 9 Interferences .......1......................................................................................................................1 Coulometry.........................3 Liquids: Characteristics ........................................................4 Example: reevaluation of side reactions .....................................79 11..................................................................................................6...............86 11........................83 11........................2 Measurement accuracy...........70 9.................5 Additional literature .................................................4......................................1.........71 9.................................................................2 Volumetric Karl Fischer Titration .......................80 11.6............................1 Organic and inorganic chemicals .............................................2 Storing the sample .......................................70 9.........................54 7.................................................83 11.....87 11.........................1 Solids: Characteristics.....3 Technical products – organic .............................................................73 10.......6................................................................................39 5........................................................3 Amount of sample .................4 Manual Karl Fischer drying oven............................................5 Determination of water in gases ..................5 Accessories for sample input ....80 11.................................................2 Foods and technical products ..........................................................58 7..............................................1 Reaction with methanol.............................................3 Titration Methods .............................................85 11......3 Repeatability .........................................1...........................6 Determination using the drying oven .............................55 7...............................................................1 Taking the sample....................................................43 6......40 6 Sample addition ...................................................................................67 8.....................................6.....4 Lyophilized substance in septum bottles.........................................................2 External extraction .6....................................................2 Purge gas........................................................................2 Liquid samples ..............87 11..................................................2.....................................2 Coulometric methods ............2........................................................89 12 Appendix ....4.................................................................................................67 8................................................2 Solid samples............................................................................................................................................................................................................................................................................71 9.....2 Reaction with water..................................................................4............71 9..47 7.....1........................1..................................................................................5 STROMBOLI automatic oven sample changer ...5 Technical natural products .................................................................................3 Procedure.....METTLER TOLEDO Good Titration PracticeTM in KF Titration 5................................................................4............................................................58 7............2 Inorganic chemicals ......................................................................................................4 Liquids: Sample input.............................75 11 Karl Fischer Titration: The Method at a Glance .................................................................................................................73 10...57 7........................................................................72 10 Troubleshooting .....................................................................................................1 Organic Chemicals................................59 7....................................................................1 Solid samples.........................................................1 Effects of temperature..1 Principle ................................1 Volumetric methods ...........1 Resolution and detection limit ...3..................................77 11..........79 11...................................2 Solids: Sample input ...............................2......

..........1 For samples that are soluble in methanol or ethanol ..............................................................................95 12.....3 Reagents for coulometry: .......................................3 For samples that are insoluble in methanol or ethanol ......................................................................................................3 Standards for Karl Fischer coulometry.....6.................................1 One-component reagent .......................................................................................2 For samples poorly soluble in methanol or ethanol......................91 12.........................................4 For ketones and aldehydes................92 12...........................................5 For acids and bases (pH value) .....................90 12................98 13...5 For acids and bases (pH value) .98 13.4 Safety data for the KF-components and auxiliary solvents: .........................................................98 13.................................4.................................4...............4 Reagents and solvents for coulometric analysis ..................................................................................93 12.................2 Two-component reagent: ...95 12.....................................................................................................95 12.....................6...............92 12..........................2 For samples that are poorely soluble in methanol or ethanol ...........................92 12........1 For samples soluble in methanol or ethanol .......................4.......6......................6..4 For ketones and aldehydes...........................................................96 12.........................5 Water Standards for Karl Fischer volumetric titration..................................METTLER TOLEDO Good Titration PracticeTM in KF Titration 12.....4.......................96 12.................................6..............................98 13..........97 13 Hazards and waste disposal tips .....98 3 ...............91 12.............3 For samples insoluble in methanol or ethanol....94 12...............1 Formula for the external extraction ........................................6 Titrants and solvents for volumetric analysis ..........2 Formula for the external dissolution .......4....................95 12.....................................93 12............

Publication on stabilized single-component Karl Fischer reagent by E. Wernimont and F. 1. METTLER TOLEDO RONDO Sample Changer with Karl Fischer Kit for automated KF volumetric determination. April 1956. Water standards (10. Use of Karl Fischer method spreads. They replaced the DL18/35 KF Volumetric Titrators.J. 2000 2001 2002 2008 4 . Enormous spread of the use of KF titration.Direct method”). M.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1 Fundamentals of the Karl Fischer titration 1.0. Introduction of the METTLER TOLEDO Titration Compact Line V20/V30 and C20/C30 Karl Fischer Instruments. Jungnickel. promoted by publications by E. Introduction of the METTLER TOLEDO STROMBOLI KF Oven Sample Changer. by G. DO185 Drying Oven for the DL18 Karl Fischer Volumetric Titrator. 0. Meyer and C. Introduction of the METTLER TOLEDO DL32/39 KF Coulometers (generating cell with and without diaphragm).Boyd [4]. Introduction of less poisonous KF reagents based on ethanolic solution. Publication: “The Dead-Stop End Point“. Improved METTLER TOLEDO DO307 KF Manual Drying Oven. First fully automatic KF titration with laboratory robots (METTLER DL18 and ZYMARK). Pyridine-containing two-component reagents and dead-stop titration instruments are commercially available.1 mg/g) with test certificate according to DIN 50049-2. titrant specific standard parameters and LEARN titration. First microprocessor controlled KF titrator (METTLER DL18) with automatic drift compensation. First coulometric KF titration instruments are commercially available. Automatic KF titration instruments with piston motorized burettes.0. S. 1959 1960 1970 1980 1984 1985 1989 1990 1995 1997 1998 New DV705 KF Titration Stand with very low drift value (< 2μg/min) for the METTLER TOLEDO DL53/55/58. L. “Testing of mineral oil hydrocarbons and solvents: Determination of water content according to Karl Fischer .3 First titrator (METTLER TOLEDO DL55) with online curves E = f(t) and V = f(t) for Karl Fischer titration. Pyridine-free KF reagents are commercially available. D. respectively. Hopkinson [2].5% and 1%. and DL67/70ES/77 Titrators Introduction of the METTLER TOLEDO DL31/DL38 KF Titrators with dedicated fuzzy logic control. Eberius [3]. Solid KF Oven Standards with water contents of 5. and solvent dispensing and removal. Peters and J. DL37 KF Coulometer from METTLER TOLEDO.1 1935 1943 1950 1952 1955 1956 An historic overview Publication: "Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern" by Karl Fischer [1]. Publication: Coulometric Karl Fischer Titration by A. First diaphragm-less cell for coulometric KF titration. First German DIN standard for the Karl Fischer titration (DIN 51777.

5. Barenrecht [7] on the subject of the Karl Fischer reaction have revealed that: • • Pyridine is not directly involved in the reaction. I2 + SO2 + 3 Py + H2O → 2. I2 + SO2 + 3 Py + H2O → 2. In order to achieve an equilibrium shift to the right. Karl Fischer used pyridine for this purpose.2 The Karl Fischer chemical reaction I2 + SO2 + 2 H2O → 2 HI + H2SO4 The water content determination is based on the reaction described by R. Bryanz and Mitchell [6] formulated a two-step reaction: 1. Py•SO3 + H2O → 2 Py-H+I– + Py•SO3 – Py-H+HSO4 – Further studies conducted by J. W. In an alcohol-free solution. it only acts as a buffering agent and can therefore be replaced by other bases. At pH values above 8.e. Verhoff and E. it is necessary to neutralize the acids that are formed during the process (HI and H2SO4). the reaction between iodine and water takes place in the stoichiometric ratio of 1:2: 1. Methanol proved to be suitable as a solvent. methanol not only acts as a solvent but also participates directly in the reaction itself. The rate of the Karl Fischer reaction. In an alcoholic solution. described by the rate constant k. all the sulfur dioxide is present as methyl sulfite. In the pH range 5. Py•SO3 + CH3OH → 2 Py-H+I– + Py•SO3 – Py-H+CH3SO4 According to these equations. the 5 . C. i.5 to 8. Bunsen [5]: Karl Fischer discovered that this reaction could be used for water determinations in a nonaqueous system containing an excess of sulfur dioxide [1]. Smith.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1. and the faster the rate of the Karl Fischer reaction. This is formed from sulfur dioxide and methanol according to the equation: 2 CH3OH + SO2 → CH3OH2+ + CH3OSO2- The higher the pH of the solution. the more methyl sulfite is formed by the capture of protons. the maximum reaction rate is reached here and cannot increase further. but rather the methyl sulfite ion.. the reaction between iodine and water takes place in the stoichiometric ratio of 1:1. depends on the pH value of the medium (see graphics below) -d[I2]/dt = k • [I2] • [SO2] • [H2O] One possible explanation for the influence of pH on the reaction rate is that it is not the sulfur dioxide itself that is oxidized by iodine under the influence of water.

for determination in ketones or aldehydes). however. If a methanol-free titrant has to be used (e. This improves the titer stability. you should adjust the pH value to the ideal range by adding buffering agents (for acids: imidazole. and references therein].3 • Consequences for practical applications Influence of pH on the Karl Fischer reaction Since the maximum rate of the Karl Fischer titration is in the pH range 5.g. Scholz resulted in the following reaction scheme being proposed for the Karl Fischer reaction [8]: 1. in a titration. for instance. Verhoff and E. Methanol should therefore always be present in the minimum required amount.METTLER TOLEDO Good Titration PracticeTM in KF Titration reaction rate increases due to side reactions between iodine and hydroxide or methylate ions. is not a serious limitation because the water concentration in the solvent is usually much less. ethanol. Scholz developed a pyridine-free Karl Fischer reagent with imidazole as base [8]. J. but also facilitated faster and more accurate titrations because imidazole buffers in a more favorable pH range than pyridine. → → (RNH) · SO3 R (RNH) · SO4 R + 2 (RNH)I 1. On the basis of this knowledge. Scholz was also able to confirm the existence of basic methylsulfite in methanol/SO2/I2 solutions during the titration. dimethylformamide) Studies by Eberius [3] showed that iodine and water react in the ratio of 1:1 if the percentage of methanol in the solvent is 20% or more. and for bases: salicylic acid). this results in a more sluggish endpoint and higher iodine consumption. 6 .g. diethylene glycol monoethylether) [10. • Influence of the water content of the sample on the Karl Fischer reaction The water content of the sample also influences the H2O:I2 molar ratio. pH values less than 4 and greater than 8 should be avoided in practice. This. methanol) (e. Barendrecht [7] observed an increase in the titer with water contents greater than 1 mol/L.C.g. In 1988. With acidic or basic samples. pungent pyridine. E. A. Seubert [9] identified methylsulfite in KF solutions with the aid of IR spectroscopy and isolated and identified methyl sulfate as the secondary product of the KF reaction. (RNH) · SO3 R + 2 RN + I2 + H2O This resulted in the general chemical equation: ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I E. ethylene glycol monomethyl ether.5 to 8. methoxyethanol. Experiments on the stoichiometry of the reaction showed that methanol can in fact be replaced by other alcohols (e. Studies by E. 2-propanol. ROH + SO2 + RN 2.g. This reagent not only replaced the toxic. you can use other alkohols such as. • Influence of the solvent on the Karl Fischer reaction The stoichiometry (molar ratio of H2O:I2) depends on the type of solvent: Alcoholic solvent Non-alcoholic solvent H2O:I2 = 1:1 H2O:I2 = 2:1 (e.

5 mg/mL per year in a sealed bottle.5% 2. sulfur dioxide and imidazole. where iodine is generated by electrochemical oxidation in the cell The selection of the appropriate technique is based on the estimated water content in the sample: Volumetric Karl Fischer Titration Iodine is added by a burette during titration.1 One-component KF reagent The titrant contains iodine. Coulometric Karl Fischer Analysis. is approximately 0. where a solution containing iodine is added using a motorized piston burette. Suitable for samples where water is present as a major component: 100 ppm . The reagent can be stored for approximately two years. 2 mg/mL for samples with a water content of less than 1000 ppm. The solvent is methanol. dissolved in a suitable alcohol. The drop in titer.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2 Volumetric and Coulometric Karl Fischer Analyses The determination of the water content according to Karl Fischer is nowadays performed by two different techniques: – – Volumetric Karl Fischer Titration. 1 mg/mL for samples with a water content of less than 200 ppm. i. 7 . Suitable for samples where water is present in trace amounts: 1 ppm .1..1 Volumetric KF reagents 2. You can also use a methanolic solvent mixture specially adapted to the sample as the solvent.e. the decrease in concentration. The reagent is available in three different concentrations: 5 mg/mL for samples with a water content of 1000 ppm to 100%.100% Coulometric Karl Fischer Analysis Iodine is generated electrochemically during titration.

from VWR/MERCK) are commercially available to prevent this problem. such as amines. increases their lifetime. and results in higher titration speed. Special methanol-free KF one-component reagents such as e. or an alcoholic mixture.1. This special reagent is also suitable for substances that react with methanol. + Simple handling. leading to higher water contents and a vanishing end point. The solvent is either methanol or consists of methanol mixtures. sulfur dioxide and 2-methoxyethanol. from Sigma-Aldrich) and e. whereas the solvent consists of sulfur dioxide and a base. The titration takes slightly longer than with the standard KF reagent. some manufacturers also sell the titrant separated into solution A (sulfur dioxide. favorably priced.4 Special reagents for aldehydes and ketones Aldehydes (R-CHO) and ketones (R-CO-R) form acetals and ketals if titrated with standard methanol-containing reagents. dissolved in methanol. Some manufacturers have slightly increased the pyridine content in the titrant to achieve a higher titration speed. provided that the bottle is tightly sealed. e. Reagents One-component Two-component 2. Two-component reagent: The titrant contains iodine dissolved in an alcohol. The separation into titrant and solvent improves stability of the KF reagents. reagents containing pyridine are still used because they are cheaper and can be made in-house.1.g.g.2 Two-component KF reagent The titrant contains iodine and methanol. HYDRANAL® (Composite 5K and Working Medium K. sulfur dioxide and pyridine. Solvent capacity restricted. whereas the solvent contains 2-chloroethanol and trichloromethane.3 Pyridine-containing reagents Despite the existence of pyridine-free reagents. To improve stability. Note that it may be necessary to adapt the end point value in the titration method to these reagents. apura® (CombiTitrant 5 Keto with CombiSolvent Keto. A titration speed two or three times as high can be achieved with the two-component reagent. The solvent contains sulfur dioxide. 8 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 2. pyridine. These solutions are mixed 1:1 just before use to form the one-component titrant. dissolved in an alcohol (usually methanol). One-component reagent: The titrant contains iodine. 2. 2 mg/mL for samples with a water content of less than 1000 ppm. stable titer. methanol). which allow for fast and accurate Karl Fischer titrations. additional water is produced and titrated at the same time. One-component reagent: The titrant contains iodine. titration speed slower.1. As a result. methanol) and B (iodine. This reagent is declared as “rapid”.g. imidazole. It is available in two different concentrations: • • 5 mg/mL for samples with a water content of 1000 ppm to 100%. – Titer less stable. methanol. Both the components are very stable in storage. High titration speed. imidazole. imidazole and methanol.g. The titrant has a stable titer. e.

the anode compartment and the cathode compartment.2. The titrant contains iodine and ethanol.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2. or “inner burette”) incorporated into the glass titration cell. ethanol-based reagents were launched in 1998.1 KF coulometry Coulometric KF determination of water is based on the standard reaction equation for the KF reaction. Both parts are separated by a diaphragm. a double pin platinum electrode. imidazole. These reagents also allow for titration of several ketones which form ketals considerably more slowly in ethanol than in methanol.5 Karl Fischer reagents with ethanol Since ethanol is less toxic than methanol. the iodine is generated electrochemically by anodic oxidation in the coulometric cell according to the following half-reaction: 2 I . two-component. * The terms "generator electrode" and "measuring electrode" mean an arrangement of two electrodes (anode and cathode) to form an electrolytic cell.→ I2 + 2 e Iodine generation occurs at a generator electrode* (also called “generator cell”. 2.1. 9 . which is monitoring the potential of the sample solution by voltametric technique during coulometric titration. however.2 Coulometric KF analysis 2. diethanolamine and ethanol. ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I In coulometry. whereas the solvent contains sulfur dioxide. The generator is close to the measuring electrode*. The classical coulometric cell consists of two parts.

→ I2 → H2O 10 .e. i. the positive hydrogen ions are reduced to hydrogen. can reach the cathode where it is reduced to a sulfide compound (obnoxious smell!). CH3SO3H. Anode reaction At the anode. iodine is generated from iodide by electrochemical oxidation. I-. the KF electrolyte which is required for the oxidation in order to generate iodine by applying a current at the generating electrode.2 Stoichiometry of the coulometric KF rection The amount of water titrated by coulometric technique is determined by the amount of electrical current given in Coulomb. 2 [RN]H+ + 2e. The value 96845 C/mol is known as the Faraday constant. To calculate it. The negative iodide ions release electrons at the anode and form iodine. An ammonium salt is added to the catholyte in order to promote hydrogen production. Note that methyl sulfonic acid. Subsequently. or the same reagent as used in the anode compartment. Methanol or ethanol is used as solvent. releasing two electrons at the anode. iodine reacts with water.METTLER TOLEDO Good Titration PracticeTM in KF Titration The anode compartment contains the anolyte. This consists of sulfur dioxide. it is necessary to first recall the definition of 1 Coulomb: one coulomb. the catholyte should be replaced once in two weeks. This is the main product formed. This can cause the cathode to become black. hexanol or ethylene glycol may be added. octanol. is the quantity of charge that is transported by a current of 1 ampere in one second. used to generate iodine. other solvents such e. 96485 C of current are needed. 2 I.g. the reagent that enables completion of the whole electrochemical reaction: the oxidation reaction in the anolyte compartment is completed by a reduction reaction in the catholyte compartment. The catholyte is either a manufacturer-specific special reagent. To avoid this. it is known that to produce one mole of a chemical substance that requires one electron. 1C=1A·1s On the other hand. I2. which subsequently reacts with water. are oxidized to one molecule of iodine.2.→ H2 + 2 RN Ammonium ions are then reduced with the formation of hydrogen and a free amine. C. i. Depending on the application. In Karl Fischer reaction two iodide ions. as chloroform. Cathode reaction At the cathode.e. 2. present in the anolyte compartment. imidazole and iodide salts. C. The cathode compartment contains the catholyte.

For this reason.METTLER TOLEDO Good Titration PracticeTM in KF Titration Therefore. the coulometer operates with current pulses of 400 mA.3 Iodine generation Iodine is generated by means of current pulses of 400. The maximum pulse height depends on the following factors: conductivity of the anolyte voltage at the generator electrode surface of the generator electrode The voltage at the generator electrode and the surface of the electrode depend on the type of coulometer. For an electrochemically optimized Karl Fischer cell. etc. This gives an iodine generation rate which corresponds to a maximum of 2240 μg water/min. the current conversion efficiency for iodine production is assumed to be 100%. less than 3–4 μS/cm). no standardization of the coulometric KF reagents is necessary. this calculation can be expressed as follows: 1 mg of water corresponds to a consumption of 10.2. it is used as a reference method for the determination of water content.4 Generator electrode without diaphragm with diaphragm without diaphragm The first commercially available diaphragmless cell for KF coulometry was introduced in 1989. 2 x 96485 C/mol is required for 1 mole of water. 2.). hexanol. 2. Nevertheless. At very low conductivities (i. The rate of iodine generation is adjusted by varying the pulse duration and frequency and the pulse height (in mA). it is strongly recommended that the coulometer is regularly checked by measuring a certified water standard. the conductivity of the anolyte is influenced by the samples and additional solvents (chloroform. In addition. 200 and 100 mA. Since current and time can be accurately measured. the maximum possible current applied by the instrument is 100 mA. As a consequence. The main advantages compared to cells with diaphragms are: no contamination or blockage of the diaphragm easier cleaning lower drift 11 . Since the molar mass of water is 18. coulometry is designated as absolute method. 300.712 C electrical current. With standard conductivity values.e.2.015 g/mol.

However. Thus.chlorinated hydrocarbons alcohols . The diaphragmless cell is ideal for the determination of the water content of the following compounds: hydrocarbons . Nevertheless. especially when easily reducible. especially for nitro compounds such as nitrobenzene. This is a very good reducing agent. etc.. the cell with diaphragm may yield more precise results.2.ethers ketones (with special reagent) . The latter can thus react more efficiently with water. Nascent hydrogen is formed at the cathode.acetamides etheric oils and essences . the cathode is a small-size pin). may also be reduced at the cathode by the formation of water. a relatively high stirrer speed allows for more rapid distribution of the generated iodine molecules. This effect is further enhanced by the small dimensions of the cathode. The cathode is smaller and made in such a way that iodine cannot reach the cathode (i. To avoid this concurring reaction.edible oils petroleum oils A cell with diaphragm is required for: samples with a very low water content (< 50 μg water/sample) very accurate determinations nitro compounds unsaturated hydrocarbons. R-NO2 + 3 H2 → R-NH2 + 2 H2O Besides this. for measurement of samples having a very low water content (e. other easily reducible substances such as unsaturated fatty acids. The purpose is to prevent that iodine molecules generated at the anode are immediately reduced to iodide ions at the cathode instead of reacting with water. the relative error due to this effect can be minimized by using a larger amount of sample. and for very accurate determinations.METTLER TOLEDO Good Titration PracticeTM in KF Titration Originally. it is still possible for a very small amount of iodine to reach the cathode. Note that hydrogen gas generated at the cathode is forming gas bubbles around its surface.e. this makes it almost impossible for iodine to reach the cathode and be reduced to iodide. 12 . 2. In addition.g.5 Limitations for the use of the cell without diaphragm The cell without diaphragm is not suitable for samples that are easily reduced. In practice. a different geometry is used for the generating cell without diaphragm. the generator cell was first built with a porous ceramic frit (diaphragm) separating the inner cathode compartment from the anode compartment.phenols (most) esters . lower than 50 μg water/sample).

When the voltage drops below a defined value. there will be free iodine in the titration solution. iodine should be added or generated as quickly as possible.the addition speed or generation rate of iodine . The resulting titration speed depends on the following factors: . The control of the titration is only possible if the end point is indicated. 3. the titration is terminated.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3 Titration control and end point determination The addition or generation of iodine must be controlled. Free iodine causes ionic conduction and the voltage needs to be reduced to keep the polarization current constant. Ideally. and hence. there is no free iodine in the titration/anolyte solution. • • • As soon as all the water has reacted with iodine.1.the viscosity of the solution and its temperature.1 Principle of bipotentiometric indication A bipotentiometric indication is used for the volumetric Karl Fischer titration as well as for the coulometric analysis (in electrochemical terminology this is also called "2-electrode potentiometry"). • • As long as the added iodine reacts with the water. . A small. Only then can the titrant consumption or the generated iodine amount be determined with the desired accuracy. A high voltage is necessary to maintain the specified polarization current at the electrode.the termination of the analysis.the reaction rate of the Karl Fischer reaction . . 13 .1 Indication 3. . constant AC current – the polarization current "Ipol" – is applied to a double pin platinum electrode. and the addition or production stopped exactly at the end point. the water content.the stirring speed and mixing of the sample solution.the control algorithm and its parameters.

Ionic conduction Iodine takes up an electron at the negatively charged platinum pin of the indicator electrode and is thereby reduced to iodide (I-). This drop in voltage is used to indicate the end of the titration. This free iodine gives rise to "ionic conduction". no iodine reaches the negatively charged platinum pin. A voltage of ca. The iodine is present only at low concentration.(to a lesser extent) the type of electrode (i. This leads to a termination of "ionic conduction" and the measurement signal becomes unstable. again. geometry and dimensions of the metal parts) . I2. respectively. At the end of the titration: As soon as all the water in the sample has reacted with the iodine.1. there is no free iodine in the titration/anolyte solution. The two negatively charged iodide ions are attracted by the positively charged platinum pin. Ipol .e.the solvent or anolyte used in the instrument. • • At the beginning and during the titration: As long as the iodine generated reacts with the water.2 End point and polarization current The Karl Fischer titration is terminated when an excess of iodine is detected in the titration cell. The end point value mainly depends on .METTLER TOLEDO Good Titration PracticeTM in KF Titration • The ionic conduction takes the following course: an iodine molecule is attracted by the negatively charged platinum pin. Iodide ions. free iodine is present in the titration/anolyte solution.e. Now a low voltage of 50 mV to 100 mV is required to keep the polarization current constant. 3. where they donate the electrons and form an iodine molecule. It then acquires two electrons and turns into iodide ions (2 I–). Above all. the titration end point is reached if the potential at the polarized platinum double pin electrode drops below a specific predefined value. then releases the electron again at the positively charged platinum pin and is again oxidized to iodine. 400 mV to 650 mV is necessary to maintain the set polarization current at the double pin electrode. 14 .the polarization current. . i. which are present in excess in the titration solution. this value depends on the polarization current. If mixing is poor. Thorough mixing of the titration/anolyte solution is necessary in order to achieve constant "ionic conduction".

its surface can easily bond suitable chemical compounds. i. Sensors with short platinum pins (< 3 mm). The layer is formed during the first ten titrations. exhibit a smaller potential jump. As a consequence. and subsequently it remains constant. a double ring or plates instead of rings. However.4 mm.e. The current density can be compared to a water pipe where a specific water has to flow. a layer is formed on the surface of the platinum pin sensor. and increases the risk of over titration. i. This makes it more difficult to stop the titration at the right moment. On the other hand. just after the equivalence point.e. With used sensors. pin diameter: 1 mm): AC Polarization current / µA 24 Endpoint / mV 100 For the coulometric KF analysis.g. 15 . The condition of the sensor has an influence on the potential jump Platinum is a strongly adsorbing metal. Sensors with a large platinum surface. The larger the diameter of the pipe. the lower the pressure needed to transport the desired amount of water through the pipe (= smaller pressure difference). With use. this leads to a larger potential jump compared to a cleaned or a new sensor (without layer). Which polarization current should be used? A higher polarization current requires a larger iodine excess (indicated by a pronounced yellow coloration of the titration cell solution) to achieve ionic conduction for the determination of the end point. exhibit a larger potential jump and also a higher end point. pin length: 3 . a lower polarization current gives a smaller and steeper potential jump at the end of the titration. iodine excess should be as low as possible to get accurate results. e.METTLER TOLEDO Good Titration PracticeTM in KF Titration For the volumetric KF titration. the following end points have been defined for methanolic one-component and two-component KF reagents using a V20/V30 volumetric KF titrator or T70/T90 Excellence titrator (double pin platinum electrode. pin length: 3 to 4 mm. and increases the sensor resistance. on the other hand. pin diameter: 1 mm): AC Polarization current / µA 5 Endpoint / mV 100 The same end point values can be used for ethanol based KF coulometric reagents. In general the larger the platinum surface the smaller the current density. the polarization current should be set as low as possible. Influence of the sensor The potential jump at the end of the titration is also influenced by the geometry (surface and design) of the platinum sensing material of the sensor. the following values have been obtained with a C20/C30 KF Coulometer (double pin platinum sensor. with longer pins.

This results in a reaction rate up to 2 times faster for the two component reagent than for the one component reagent.and on the iodine concentration. On the other hand. [I2] .2 min with a titrant consumption of 2. irregular. If 16 .5 . In the volumetric KF titration. It is consumed with each additional measured sample leading to a decreasing dioxide concentration.2 Reaction rate The reaction rate of the Karl Fischer titration depends on: .0 mL 1. a large excess of sulfur dioxide is present in the solvent. At the beginning. 3. the water content is high. 3. and the reaction rate also decreases: iodine must be generated or added more slowly because a small water amount is still present. and overtitration may occur. note that sulfur dioxide is added only in slight excess with the iodine titrant solution when using one component titrant.d[I2] / dt = k · [I2] · [SO2] · [H2O] In addition. the water concentration is lower. Example (V20/V30/T70/T90): One-component reagent Two-component reagent 2-3 min with a titrant consumption of 2. point of titrant addition (volumetric KF titration). which gives a high reaction rate.the water concentration. Iodine generation or addition is usually the rate determining factor. Stirring speed The optimum stirring speed is obtained when a distinct vortex is visible. stirring speed.0 mL In the coulometric KF analysis. As a consequence. 2. sulfur dioxide is present in large excess in the anolyte.3 Stirring speed and dispersion of the volumetric KF titrant Good mixing is essential for fast and accurate KF titrations. Iodine generation or addition can proceed rapidly because iodine immediately reacts with water. the titration may also be too slow. shape of the vessel (volumetric KF titration). [SO2] .METTLER TOLEDO Good Titration PracticeTM in KF Titration 3.the sulfur dioxide concentration. [H2O] . lower reaction rates are achieved with anolyte solutions that have been used for a long time. Karl Fischer titrations with the two component reagent are thus significantly faster than with the one component reagent. Towards the end of the titration. the pH value of the solution has a strong influence on the rate and in particular on the stoichiometry of the Karl Fischer reaction. Mixing is influenced by the 1. with the twocomponent reagents. If the speed is too slow.

Vessel shape The conical shape of the beaker and the short stirring bar lead to turbulence at the point of titrant addition that effectively disperses the titrant. Otherwise the sensor may directly detect added iodine. the point of addition should be sufficiently far away from the sensor to allow for sufficient time for reaction. turbulence is not achieved and the mixing effectiveness is lower. but rather along the base directly towards the sensor. 17 . This is essential for a fast reaction rate and for short titration times. Iodine would not be distributed upwards. Bubbles falsify the measured values. the stirring speed is too fast. Point of titrant addition The titrant should be added where the turbulence is the greatest to ensure efficient mixing. leading to slower addition and longer titration time. Furthermore.METTLER TOLEDO Good Titration PracticeTM in KF Titration bubbles form into the solution. If a longer stirring bar is used.

1 The Control Band The control band is a modifiable control parameter for both types of KF reagents.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. An overview of the control parameters is given as follows: Volumetric KF Titration End point Control band Dosing rate (max) Dosing rate (min) Start: Normal. Cautious The volumetric KF methods of the V20/V30 as well as T70 and T90 use KF titrant specific titration control parameters. The recommended standard values are listed in the following table: Recommended standard values Sensor Ipol [µA] Stirrer speed [%] End point [mV] Control band [mV] Dosing rate (min) [µL/min] Dosing rate (max) [mL/min] Start Driftstop relative [µg/min] 1-Comp titrant 24 35 100 400 80 5 normal 15 2-Comp titrant 24 35 100 400 100 3 normal 15 3.4 Control parameters in the volumetric KF titration Several parameters can be defined in the titration method in order to optimize the method for the samples and the reagents. The following drawing reveals a schematical illustration of the control band: 18 .4. The dynamic behaviour of the control can be influenced by a variation of the control band.

g.The dynamics of the control can be influenced in the following way: Increase of the control band Aggressive control Smooth control Two different controls are used for 1-Comp and 2-Comp titrants. 3. Thus.4 Polarization current and end point Each end point is valid for a specific polarization current. if the polarization current changes. Dosing rate (max) = 2 mL/min. 3. at higher water contents. which leads to a stronger reduction of the dosing speed. The 2-Comp titrant control reacts more sensitively to a potential drop than the 1-Comp titrant control. The closer the potential to the end point. longer titration times and poorer repeatability are resulting by selecting a higher end point potential value. the end point must be adjusted.3 The Cautious start If the water content is very low. sensors with very short platinum pins (< 3 mm). the slower is the titrant addition.METTLER TOLEDO Good Titration PracticeTM in KF Titration The titrant addition is calculated on one hand by using the distance of the actual potential from the end point and on the other by using dE/dt. the titrator automatically issues a warning.2 The minimum and maximum dosing rate Both rates limit the dosing speed of the titrant to an upper or lower level. i.e. With large amounts of water. This is more suited for small water amounts. 3.. the control reacts more sensitively to potential changes. the titration starts so quickly that overtitration may occur. 19 . the titration will take too long. In both cases (normal and cautious mode) the maximum dosing rate will be reached at the end of the ramping up. The following points represent possible contributing factors: contaminated or old sensors. The end point for a specific polarization current is influenced by the sensor and the solvent.4. however. The maximum dosing rate is dependent on the actual burette size. Recommendations 1. Burette size [mL] 1 5 10 20 Maximum dosing rate [mL/min] 3 15 30 60 Remark: Since the maximum dosing rate of a 1 mL burette is lower than the standard parameter 5 mL/min in the case of a 1-Comp titrant. In this case you can activate the Start: Cautious parameter. the titration starts with a slower acceleration (ramp up) than in the normal mode.4. if the control band width is decreased.4. In the cautious mode. 2. e. You should select Start: Cautious for one and two component reagents if the amount of water in the sample is less than 500 µg. In particular. You can also set the maximum dosing rate to a lower value for small amounts of water if you wish the titration to progress more cautiously.

• If 1-comp titrants are used. setting up of the titrant as 1-comp KF titrant yields shorter titration times. the overall ionic conductivity is decreased. instead of methanol or ethanol. the titration curve is more or less flat towards the end. e. 3.METTLER TOLEDO Good Titration PracticeTM in KF Titration - long alkyl chain alcohols. used as solvent. the sensor current shall be reduced to 15 μA. Therefore the potential jump at the end of the titration is smaller compared to conventional reagents. which will lead to long titration times and to low precision.g. Therefore it is recommended to decrease the polarization current to about 15 μA. • • If 1-Comp titrants are used with Ethanol (e. Ethanol-based reagents • Compared to the methanol-based reagents. the titration can be accelarated by reduction of the control band to 300 mV. Composolver E) the standard 1-Comp parameters (cf. The consequences of choosing a too low end point value are illustrated in the figures above: On the right side. table) work fine. the control band shall be decreased to 100 mV and the maximum dosing rate decreased to about 50%. 20 . the overall ionic conductivity is increased. If one-component reagents are used. In order to achieve a good repeatability. This results in a lower voltage required to maintain the polarization current. 2-propanol. this results in an illdefined titration end point.g.5 Application tips Methanol based reagents • The standard parameters listed in the table above are ideal for the titration with methanol-based reagents. up to 8 mL/min for most 2-Comp 2 titrants. This measure allows the system to cope with the reduced conductivity.4. • If 2-comp titrants are used. the system reacts slowly in the case of ethanol based reagents. • If Chloroform or Xylene is added in order to dissolve oil samples. the maximum dosing rate can be set higher for certain reagents: 4 mL/min for Riedel de Haen 2-Comp 5. Auxiliary reagents • If formamide is added to the solvent. If 2-comp ethanolic reagents are used.

In most cases 300 – 400 mV are well-suited. an increase of the control band is recommended.4.METTLER TOLEDO Good Titration PracticeTM in KF Titration KF reagents for ketones • An end point value of 150 mV for both one-component and two-component reagents is recommended when using special KF reagents for aldehydes and ketones. Furthermore it is recommended to reduce the polarization current to a value of 15 μA. If the titration takes too long. 3.g. In the case of 2-comp reagents over titration can be prevented by reduction of the maximum dosing rate.5 Control paramaters in the coulometric KF Analysis An overview of the relevant control parameters is given as follows: End point Control band Rate: Normal.6 General recommendations 1. There is no need to accurately adjust the control band to the actual start potential. where the methanol has been replaced by e. 100 mA) 21 . 200. However the control band shall not exceed the start potential. 3. which is the case in 1-Comp systems. E E t Oscillating system behaviour. 2-methoxyethanol. ->Use the 1-Comp control Smooth system behaviour ->Use the 2-Comp control t 3. Cautious Generator current: Automatic. 2. The most straight forward influence on the control behaviour is achieved by a variation of the maximum dosing rate. Fix (400. the 1-Comp control is suitable for systems that show an oscillating potential behaviour. 300. The minimum dosing rate shall be used to fine tune the final phase of the titration. This control is also recommended for 2Comp systems that show a noisy signal at the beginning of the titration. In general. which is the case in some ethanolic reagents.

In particular. i. Variation of pulse length (time). or it can be set to a specific value (“Generator current” . The iodine generation starts slowly. The closer the measured potential value from the predefined end point is. the iodine generation is higher than in the cautious mode. 3.Fix). During the course of the titration it increases up to the maximum rate at a generating current of 400 mA. the slope of the iodine generation is steeper and the rate is increased based on the measured potential value. absolute drift stop. This parameter shortens the titration time and leads to repeatable results. pulse frequency and pulse height (mA) are used as variables by the instruments. the online determination of the drift during analysis has enabled a so-called "drift stop" to be used as a termination parameter. Initially. a delayed switch-off time of 10 to 20 seconds was set at the end point. 2. iodine is generated by means of current pulses of 400. Since the first developed KF reagents reacted slowly. the pulse height can be automatically changed by the system if in the titration method the control parameter “Generator current” is set to “Automatic”. tightly sealed stand).e. Normal: This iodine generation mode is generally used for all water content determinations.25 µL for a 5 mL burette). 200 and 100 mA. maximum titration time. high resolution burettes (0.. pyridine-free reagents with a faster reaction rate.g.METTLER TOLEDO Good Titration PracticeTM in KF Titration The iodine generation rate in the C20/C30 Coulometric Compact Karl Fischer Instruments depends on the distance from the end point.6 Termination parameters for both coulometric and volumetric KF titration The KF titration can be terminated using various parameters. less than 50-100 μg water per sample). then the titration was stopped. 300. i. In addition. the slope of the iodine generation rate is flat at the beginning of the titration. and improved KF titration stands (i. More specifically.e. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA.e. minimum titration time 22 . relative drift stop. i.e. Later on. Five termination parameters can be defined in the titration method: delay time. Cautious: Suitable for samples of low water content (e. as soon as the was potential value was lower than the set end point during the defined delay time. The coulometer provides two different modes for iodine generation under the control parameter “Rate”: 1. The fixed setting is used for solutions that exhibit a difficult characteristic with respect to conductivity. the slower is the generation of iodine. it has been possible to reduce the delay time to 5 to 10 seconds due to the introduction of • • • new.

Typical absolute drift stop value: 3 µg/min (coulometric). After the defined time has elapsed. The smallest increment must be sufficiently large to compensate the drift. easy to understand (volumetric). 23 . 5-15 μg/min (volumetric) • Advantage: independent on the initial drift. has to be t/s • Relative drift stop The titration is terminated as soon as the actual drift drops below the sum of the initial drift (i. • Advantage: This parameter ensures a high repeatability of the results.e. the titration is terminated and the result is printed. especially if working with the KF sample oven.g.Maximum titration time The titration is terminated after the defined time. otherwise the termination criterion is never satisfied. 10 µg/min (volumetric) • Advantage: Independent on the titrant concentration. Absolute drift stop Termination occurs as soon as the actual drift drops below the predefined absolute drift value. titrant concentration (volumetric) and side reactions. the absolute drift stop value must be greater than the initial drift. . 15 s) following the addition or generation of iodine. Typical delay time: 5 . Disadvantage: The minimum rate must be adapted to the initial drift and the titrant concentration. Disadvantage: The value optimized to the initial drift. otherwise the termination criterion will never be reached.m the drift before titration) and the relative drift.METTLER TOLEDO Good Titration PracticeTM in KF Titration Delay time The titration is terminated when the potential remains below the end point for a defined time (e.15 seconds (Coulometric/Volumetric) • • Advantage: well-known method. Typical value for the relative drift stop = 2-5 μg/min (coulometric). Thus.

A relative drift stop of 20 to 40 µg/min shortens the titration time without affecting the repeatability. Thus. • Advantage: This parameter ensures a high repeatability of the results. This parameter is independent of the the initial drift (coulometric.1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration The following termination criteria are most commonly used for water determination by Karl Fischer titration: Relative drift stop for trouble-free. possibly resulting in poorer repeatability and lower water contents. The reason for this is either a very slow release of the last traces of water or a slow thermal decomposition of the sample. but involves a risk that the titration will be terminated a bit too early. If the water content is relatively high. the drift at the end is often greater than the initial drift. This is particularly critical in connection with the "slower" reagents for ketones and aldehydes.e. this is the simplest and most universal parameter to use. This termination parameter is also well-suited when the internal extraction is needed to determine the water content in insoluble sample: The water contained in insoluble samples is extracted during the titration.Minimum titration time Titration is not to be terminated before this time in [s] is reached (exception: the maximum volume has been reached). The vaporization of water is also irregular in the final stages. i. you can terminate the titration at a higher drift (relative drift stop = 40 to 70 µg/min). It is recommended to be used for substances that release water slowly.METTLER TOLEDO Good Titration PracticeTM in KF Titration . soluble samples You should normally choose the relative drift stop as a termination parameter. you can ignore these traces. and the titrant concentration (volumetric). the following values are recommended for volumetric KF titration: One-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. Two-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. volumetric). so 24 . Use the drift/time curve to determine this value. 3..6. The value of the relative drift stop influences the repeatability and the titration time: • • Drift stop (low value) → better repeatability poorer repeatability → → long titration time short titration time Drift stop (high value) → In particular. A relative drift stop of 20 to 30 µg/min shortens the titration time. The final traces are only extracted very slowly. Maximum titration time for determinations with the KF drying oven When using the drying oven.

(Set the minimum titration time equal maximum titration time). Note: To obtain accurate and reliable results you should only work with the coulometer when the drift is lower than 10 µg/min. If the drift stop value is not reached. Therefore. A combination of the relative drift stop and the maximum titration time has proved effective for such samples. This is the case with samples that only release the final traces of water very slowly or that produce side reactions. you should take measures to reduce the drift. the titration is terminated at the latest after the defined maximum time. It gives you the best accuracy and repeatability of results. the maximum titration time has proven to be best termination criterion in practice. 25 . The higher drift is therefore influenced to a large extent by the sample. Relative drift stop/maximum titration time for problematic samples Some samples lead to a high drift value at the end of the titration. If the drift is greater than 10 µg/min.METTLER TOLEDO Good Titration PracticeTM in KF Titration that the repeatability of the titration termination using the drift stop parameter is poor.

The desiccant absorbs the moisture and protects the titration cell against the ingress of moisture.3 hours.1. the greater is its influence on the results of the Karl Fischer titration. Silica gel can be regenerated over night at 150 °C.e. whereas molecular sieves require temperatures up to 300 °C. however. The drift. the relative humidity increases. The air-conditioning system should therefore be equipped with a moisture condenser. since cold air cannot absorb as much moisture. remains high because the moisture present on the glass walls and the air in the titration cell diffuse only slowly into the anolyte (solvent). Briefly. 26 . In this way. the higher the atmospheric humidity in the laboratory. The Karl Fischer titrator should never be installed close to a ventilator of the air conditioning system! 4. • Protect the titration cell with a desiccant (3 Å molecular sieve and silica gel). i.1 Titration stand The titration stand must be sealed as tightly as possible against atmospheric moisture.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. This can take 1 . The following rules should be observed: • • Close all openings in the titration stand. until it is absolutely free of water. The air within the titration vessel also contains moisture. The assumption that air-conditioned rooms have a lower atmospheric humidity is often not true: the majority of air-conditioning systems simply cool the air. the titrant and the titration stand. Do not shake too vigorously to avoid solvent gets on the cover of the vessel. Moisture can enter the sample. The Karl Fischer titration Various factors must be taken into account with Karl Fischer titration to obtain correct results. The total moisture can be titrated more quickly by gently moving the vessel from side to side so that solvent swirls up the side of the vessel to pick up moisture adsorbed on the glass walls. The drying capacity of the desiccant is limited and it depends on the humidity and can be exhausted after 2 . it is titrated to dryness during pretitration. This problem is particularly relevant in tropical climates or in coastal regions. After the anolyte (coulometer) or the solvent (volumeter) has been added. the residual moisture dissolves more rapidly into the anolyte (solvent).4 weeks (indicated by a colour change of the indicator of the silica gel). When you assemble the titration stand for the first time. However.1 The influence of atmospheric humidity (drift determination) Atmospheric humidity represents the most relevant source of error in Karl Fischer titration. Condition the titration cell before use. there will be moisture on the glass surface of the titration cell and the inserts. The factors include: • • • • the atmospheric humidity the working medium the pH of the sample the side reactions between the sample and the Karl Fischer reagent 4. where the relative humidity can achieve values of more than 80%.

In this respect. On the other hand. At the start of a sample titration.(drift * titration time). traces of water will always find a way into the titration cell.2 The drift No titration stand is completely water tight. this water amount is also titrated during analysis. the drift value should therefore be as low as possible and stable before the start of a titration! 27 . the KF titrator continuously titrates the water that diffuses into the cell. or a fixed value can be defined into the titration method (“Fix value”). This is achieved by titration of the dry solvent for a defined time (drift determination). In the standby titration. Therefore it must be taken into account when calculating the water content. or it can be entered by the user (“Request”): Source for Drift Online Determination Fix value Request Explanation Last measured value of standby The drift is determined and stored as raw result DRIFT A fixed value is defined into method The value can be entered immediately after starting sample titration The drift value is subsequently used in the calculation of the result in order to compensate for the moisture that entered the titration cell according to the following formula: Sample result = Total amount of water determined . it is also possible to use the value of a previously performed drift determination (“Determination”). and its value is displayed on the screen. For accurate results. t. if it is defined as the parameter “Source for drift: Online” in method function “Titration stand (KF stand)”. On the other hand. the last measured drift value is automatically stored. and is given in μg water/minute. it is necessary to quantify the amount of water entering the titration cell during titration. Therefore. the drift indicates the quantity of water that enters the titration stand over a defined period.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4.1.

First transfer 5 mL catholyte to the cathode compartment.Then fill the anode compartment with approx. The catholyte can be dehydrated with a few drops of a volumetric KF one component titrant. the anolyte should be topped up from time to time with anhydrous methanol. a flow occurs from the cathode compartment to the anode compartment. 28 . 2.Make sure that the level of the anolyte is approx. . you must add some methanol or sample so that the color changes to yellow. 3 . In this case.Take approx. Normally this brown coloration disappears on filling the titration cell because the iodine excess is consumed.2. 2.5 mm higher than that of the catholyte. • Titration cell with diaphragmless generator electrode . when the drying oven is used.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. which leads to a higher drift. If the level of the catholyte is the same or higher. Note: In production.1 Filling the coulometric cell • Cell with generator electrode with diaphragm .Pour approx. 100 mL electrolyte solution (anolyte) into the titration cell. . If this is not the case. 100 mL anolyte. the levels slowly become the same. However.5 cm into the electrolyte solution. some anolyte solutions contain an excess of iodide and the solution has a brown colour.The difference in level between the anolyte and catholyte is maintained as long as the stirrer is in operation. 5 mL from the bottle with a syringe and inject it into the generator electrode or empty an ampoule of catholyte into the generator electrode. the moisture enters the diaphragm and is slowly released into the anode compartment. As soon as the stirrer is switched off. The catholyte always contains traces of water. By ensuring that the level of the anolyte is higher than the one of the catholyte. . .When a sample is injected into the anode compartment. This can be avoided as it follows: 1. the level of the anolyte drops due to evaporation. . the level of the anolyte increases.2 Working with the coulometric KF instruments 4.The generator electrode should dip approx. Higher anolyte level → low drift Lower anolyte level → drift is high .

After being used for two weeks. With poorly soluble samples. In practice. the worse the stirring efficiency will be. .3 Secure draining and filling of the titration cell: SOLVENT MANAGER The easiest and secure way of draining and filling the coulometric titration cell is performed with the external KF liquid handling device Solvent Manger.2. the dissolving capacity of the anolyte (coulometric KF) is exhausted and an emulsion is formed. In the cathode compartment sulfides and mercaptans are formed that lead to an obnoxious smell and a higher drift.Catholyte solutions (5 mL): after 200 mg water. If the drift is too high. The Solvent Manager is located on top of the waste bottle and includes strong air pump (diaphragm pump) and an electromagnetic valve.2. it is common use to replace both the anolyte and catholyte at the same time If after adding samples. The capacity is monitored by the coulometers (see operating instructions). Any contact with the reagent is avoided during draining and refilling of the titration cell.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. . A level sensor in the waste bottle prevents from overflow. The working principle of the Solvent Manager is illustrated in the following schematical illustrations: 29 .Anolyte solutions (100 mL): after 1000 mg water. the level of the solvent or the anolyte exceeds the 150 mL mark. This can lead to wrong results. and the risk of over titration increases. If the conductivity of the anolyte drops to a very low value.g. It is fully controlled by the titrator. • • • • • 4. This can happen if large amounts of samples of low conductivity are titrated. e. If an electrolyte is used for a long period without replacement. the drift slowly increases. below 10 μS. If an emulsion forms in the anode compartment.2 When do you have to replace the electrolyte? The electrolyte must be replaced in the following situations: • If the capacity of the electrolyte is exceeded. The higher the level in the anode compartment. when using a generator electrode with diaphragm.

30 . Step 2: The Anolyte is drained into the waste bottle by applying vacuum. Step 1b: Start the reagent replacement either from the manual function ‘Replace reagent’ or from a predefined Shortcut on the Home screen of the Touchscreen.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 1a: Put the draining and reagent refill tube into the coulometric titration cell.

In this configuration only draining of the titration cell is possible. The Solvent Manager is part of the standard delivery of the C20 and C30 Compact coulometric KF titrators. Depending on the type of the generator cell the following liquid handling actions can be performed: Diaphragmless generator cell: Replacement of the anolyte Generator cell with diaphragm: Replacement of the anolyte and draining of the catholyte 31 . An optional reagent exchange set consisting of tubes. Step 4: After a predefined time or by manual interaction the pressure within the solvent/anolyte bottle is relieved by switching the magnetic valce into the initial position. drying tube and tube holder enables both draining and refilling.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 3: The pump direction is switched by activation of the magnetic valve and subsequently fresh solvent is pumped into the titration cell by applying over pressure of dry air.

This procedure should be repeated at least once. since it would cause a higher drift value. • Thorough cleaning of the generator electrode If the generator electrode and the diaphragm are strongly contaminated.4 Cleaning the coulometric KF titration cell The titration cell and both electrodes should be cleaned.Place the empty generator electrode in anhydrous methanol. then with anhydrous methanol and dry it as described above. Simple cleaning and drying of the generator electrode Method A: . • Cleaning the titration vessel Clean the titration vessel with water or a suitable solvent. The procedure is identical to that described above.METTLER TOLEDO Good Titration PracticeTM in KF Titration Note: The tubes for anolyte exchange are not left in the titration cell during titration. Moisture and contaminants are rinsed out of the diaphragm. It provides the following: Monitoring three reagent parameters Usable life in days Capacity in mg water Number of samples When due. The C30 provides a reagent monitoring routine which is called Reagent Control. . reagents can be replaced directly out of running method Choice of enforcing the user to replace it immediately or ask again later 4. Drying is not necessary if you use it immediately. the most effective cleaning agent is chromic acid. which leads to a higher drift. especially if dirty samples are analyzed. Methanol flows through the diaphragm and rinses out moisture and contaminants. The generator electrode with diaphragm must be cleaned periodically because contamination accumulates in the diaphragm over a longer period of time.Methanol flows through the diaphragm into the cathode compartment. The contaminants can originate from samples or are side products that have been formed in the cathode compartment by reduction. . If immediate use is required rinsing with anhydrous methanol shall be applied. Method B: . Afterwards thoroughly rinse the generator electrode with water.Afterwards dry the generator electrode at a maximum temperature of 50 °C in an oven or with a hot air dryer. Place the empty generator electrode in the chromic acid or fill the generator electrode with chromic acid and let it flow through.Fill the generator electrode with anhydrous methanol. • 32 .2. . Afterwards dry the vessel at 100 °C in an oven or with a hot air drier.

We recommend to determine the titrant concentration daily. so that there is a sharp drop in concentration.3. 4. As already described. However. The volumetric KF titrators enable monitoring of the usable life and life span of the titrant. A significant change in temperature may occur: The Karl Fischer titrants consist of approximately 90% methanol or ethanol. 4. a weekly titer determination would be sufficient (the concentration of the one-component titrant changes by 0. and let an electrical current of about 400 mA flow across the platinum pins for 60 s by starting the KF titration: 1) Disconnect the S7 connection of the indication electrode. This leads to a higher potential jump.3 Volumetric KF Titration: Titrant concentration The titrant concentration can change due to the following reasons: 1.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. Their volume increases considerably with temperature.if the desiccant on the titrant bottle is "used up". The layer should therefore not be removed by cleaning. In the global settings within the setup menu of 33 . In countries where the temperature varies considerably during the course of the day and the lab is not air-conditioned. e. • Clean the platinum pin with a paper tissue. the indicating electrode does not need cleaning.g.5 Cleaning the measuring electrode Generally. it is better to determine the concentration every 2 to 4 hours. which prevents a good indication.5 mol/L sulfuric acid. This test of the complete system by a titer determination is therefore an essential condition for accurate. The titrant may absorb moisture from the atmosphere reducing its concentration (the anhydrous methanol in the titrant is very hygroscopic) . the one-component titrant. 2) Connect the S7 connection of the generator cell with the indication electrode. The titrant is not chemically stable.2. In this case.if the titrant bottle is not tightly sealed. 3. • With heavily contaminated electrodes. Based on the chemical stability of the titrant. The tightness of the titration stand and the proper functioning of the burette and the end point indication are also checked at the same time as the concentration is determined. The Ohmic resistance of the electrode is increased. while the two-component titrant is rather stable). samples may be deposited on the surface of the electrode. repeatable results.01 mg/mL per week. the tightness of the titrant bottle and the desired level of accuracy. This is sufficient in most cases. . the measuring electrode must be cleaned. a layer is formed on the platinum surface after the first few titrations. 3) Stop the method when the cleaning is finished so that the polarization current at the indication electrode is stopped.1 How often should the concentration be determined? How often the concentration is determined depends on the choice of titrant. 2. place the electrode in 0. This also becomes noticeable through a dark coloration of the anolyte at the end point. A reminder can be set to warn the user at the start of every titration that the usable life is about to expire in the predefined time range (days).

3. thus the titrant concentration slightly but continuously decreases slightly when left to stand for a long time. Determine the concentration under the same conditions as for sample analysis. Mix for 3 minutes to achieve complete dissolution before you start the titration. - 34 . Rinse the burette 2 times into a waste bottle before you determine the concentration.04 and 0.66% of water.Use the optimized METTLER TOLEDO method M301 Weigh between 0. The plastic tubing is not absolutely water vapor-tight. i. you should first grind it to a fine powder before using it or use special Di-sodium tartrate dehydrate for Karl Fischer Titration Procedure .e. which prevents the execution of further titrations.08 g di-sodium tartrate dihydrate with the aid of a weighing boat. Determine the weight by back weighing and enter it as sample size.2 Concentration determination with di-sodium tartrate dihydrate General Di-sodium tartrate dihydrate. Make sure that nothing adheres to the beaker wall or to the electrode. Na2C4H4O6•2H2O (M = 230.3 to 2. This sample size yields an optimum titrant consumption of 1.and at the same temperature. 26-50 % of burette volume. Note: 1. is the primary standard for Karl Fischer titration since it is stable and non-hygroscopic. .METTLER TOLEDO Good Titration PracticeTM in KF Titration the titrator actions can be defined that will be applied if the usable life or life span is actually exceeded. i. Add it into the titration vessel. Under normal conditions.08 g/mol).using the same titration stand with the same volume of solvent.: . Either the user is simply warned or the usage of the expired titrant is blocked. it contains 15.e. 4.5 mL with a 5 mL burette. Since it slowly dissolves in methanol. 2.

mixing time 5 minutes. The values obtained are approximately 10% too high.0 mg/g General Water standards consist of a mixture of organic solvents containing a specific amount of water. e. You can perform eight determinations in 40 mL of this mixture before you need to change the solvent.g.05 g di-sodium tartrate dihydrate). Less soluble. mixing time 2 to 3 minutes. In Solvent*/chloroform mixture 1:1 or Solvent*/decanol mixture 1:1 In Solvent*/formamide mixture 1:1 In methanol In methanol/chloroform mixture 1:1 or methanol/decanol mixture 1:1 In methanol/formamide mixture 1:1 In solvent for aldehydes and ketones (one-component reagent) In ethanol *Solvent: solvent for the two-component reagent 4. You must perform the determination in pure methanol! Less soluble. They are thus protected against the ingress of moisture and can be stored for up to five years. A cloudy solution will falsify the results (i.METTLER TOLEDO Good Titration PracticeTM in KF Titration Solubility of di-sodium tartrate dihydrate Di-sodium tartrate dihydrate must be completely dissolved (clear solution!) to obtain correct results. Slightly soluble. you should weigh in 1. You can perform six determinations in 30 mL of Solvent* before you need to change it. Highly soluble. mixing time 1 minute. Partially soluble.0 to 1.3. You cannot perform more than three determinations in 40 mL of methanol (with 0. 30% too high.3 Concentration determination with Water Standard 10. This content is confirmed by the test certificate enclosed with every package. "HYDRANAL®-Water Standard 10. The values that are obtained are approx.05 g di-sodium tartrate).045 g di-sodium tartrate).0. You can only perform one determination in 50 mL of 1:1 mixture (with 0.e. The water standards are supplied in glass ampoules. Partially soluble. Thus. You must either change the solvent after every sample or use pure Solvent* for the determination.5 g of water standard 10. You cannot perform more than one determinations in 40 mL of ethanol (with 0. mixing time 1 minute. mixing time 1 minute. You must perform the determination in pure methanol! Highly soluble. too high titer). mixing time 2 to 3 minutes. 35 . Procedure To achieve an optimum consumption of 2 to 3 mL titrant with a concentration of 5 mg/mL. always take into account the limited solubility of di-sodium tartrate dihydrate in the most commonly used solvents for Karl Fischer titrations: In Solvent* Highly soluble.0" from Sigma-Aldrich® with 10 mg water in 10 g standard.

5 mL at a time as an aliquot. or with a 10.0 µL deionized water with a 10 µL syringe. Inject exactly 10. 4. In an open ampoule the liquid standard is exposed to air moisture. the water content is increased and thus this will falsify the results. The content of an ampoule is sufficient for 3 to 5 determinations. Start the titration without any mixing time. Draw the whole content of the ampoule into the 10 mL syringe. Procedure – – You should weigh between 10 and 20 µL of deionized water or water according to ISO 3696 to achieve a consumption of 2 to 4 mL titrant with a concentration of 5 mg/mL. You can use a water standard with 1. Start the titration without any mixing time. 4. accurate results.0 mg water/g for a titrant concentration of 2 or 1 mg/mL. 2. This is due to the very small amount of sample (10 to 20 µL) that has to be injected.3. Inject 1 to 1. it is strongly recommended determining the concentration either with di-sodium tartrate dihydrate. 3. Glass syringes are better. Rinse a 10 mL syringe with approximately 1 mL of water standard. The error is minimized by rinsing and conditioning the syringe beforehand. with a Hamilton microliter syringe). Plastic syringes may introduce a small amount of moisture. – – – 36 .g. Open the ampoule shortly before the measurement in accordance with the enclosed instructions.01 mg (e. Determine the weight by back weighing. The sample should be weighed either using a balance with a resolution of 0. the whole content of the ampoule is completely drawn into the syringe. A balance with a resolution of 0.4 Concentration determination with pure water General When using pure water to determine the concentration. 5. Thus.1 mg does not satisfy the requirements for a repeatable titration. To reduce the influence of the atmospheric moisture.g. Enter 0. Use a new ampoule for each new concentration determination.0 mg/g water standard.METTLER TOLEDO Good Titration PracticeTM in KF Titration – – – – – – Notes 1. Use the METTLER TOLEDO method M300 The water standard is highly soluble in all commonly used solvents for Karl Fischer titration and can therefore be used without restrictions. METTLER TOLEDO XP205 balance) or with a 10 or 20 µL precision syringe (e. a very good deal of practice and precise working is required to obtain repeatable. 6.01 g as the sample size.

salicylic acid Foods: honey.0 µL. fat Oils: edible oil. You can use mixture of solvents to achieve complete dissolution. the sample must release water completely. noodles. Always use a syringe with a long metal shaft. tar products. ester Organic products: urea. jelly bears Starch products: flour. potato chips Chloroform Decanol Octanol Hexanol Dodecanol Toluene Formamide 70% 50% 50% 50% (30%) 37 . corn. massage oil. caramel. transformer oil. amount 100% Samples Solvents: toluene. the largest part of the solvent mixture must always be an alcohol (most preferably methanol) to ensure that the Karl Fischer reaction is strictly stoichiometric. fatty creams Waxes. It is possible to determine the titrant concentration with water in all the solvents commonly used for Karl Fischer titration. Always add each sample in exactly the same way. You can get rid of any bubbles in the syringe by expelling the water rapidly. beverages Cosmetics: soaps. Adjust the plunger to exactly 10.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. Solvent Methanol Max. 2. creams. Do not warm the syringe. Only freely available water undergoes reaction with the Karl Fischer reagent. kerosene Pharmaceutical products: ointments. suppositories Sugar products: jelly. dioxane. it may draw water out of the needle!). wipe off any drops that have adhered to the needle with two fingers (be careful if you use a paper towel. After setting the volume.3. alcohols. However. Insert the syringe through the 1 mm hole of the three-hole adapter. All the screws in the syringe must be tightened securely. ethereal oils Petrochemical products: gasoline. emulsions Petrochemical products: crude oil. You should always observe the following points when determining the concentration with a 10 µL syringe: Precondition the 10 µL syringe for approximately one hour by filling it with water.5 The solvent To determine the water content in a sample. diesel oil. to avoid touching the glass part. yogurt. if it is absorbent. - 4. lay it down on the adapter and empty it completely. hydraulic oil. Hold the syringe at right angles directly in front of your eyes to read off the value.

METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. 4. Therefore. The Compact Line KF titrators are able to monitor the solvent capacity: the user can define when the solvent should be replaced by specifying the usable life.imidazole is used for acidic samples. it is necessary to replace the solvent timely. On the other hand. The amount of formamide at 50 °C should not exceed 30%. the titration of subsequent samples will then be very slow.salicylic or benzoic acid for basic samples. which may be completely expended if you titrate a large number of samples with high water content.6 Dissolving capacity of the solvent The dissolving or extraction capacity of the solvent is a crucial factor in Karl Fischer titration.3. If exhausted. If acidic or basic samples are titrated. The titrator accumulates the total water amount continuously during titrations and reports "Solvent capacity exhausted" as soon as the specified value is exceeded. formamide effectively extracts water from starch products. 38 . the amount of water in mg which has been titrated. 3. or by indicating the maximum number of samples to be titrated. Sugar is the only type of sample that dissolves in formamide. or the stoichiometry of the Karl Fischer reaction will change and the results will be wrong. the water will no longer be completely released. you must replace the solvent timely. The solvent for the two-component reagent contains SO2. The extraction capacity can be improved by increasing the temperature (e. starch products will not dissolve in it. or the titration will take too long and titrant will be wasted. buffering agents are first added to the solvent to ensure that the titration is quick and without side reactions: . 2. too low water content. This will lead to incorrect results. Once again. 50°C). i. The solvents that are used should contain as few water as possible (< 100 ppm). and . In this case.g.e.

With liquid samples that do not dissolve water such as oils. The sample must be representative. i. the sample should be larger the more heterogeneous the distribution of the water.g. you should determine its water content as soon as possible. Use sample bottles with small openings to minimize the ingress of moisture. and thus air moisture can penetrate the plastic and absorbed by the sample.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5 Sampling 5. you will no longer be able to determine its true water content. 3. keep it in a tightly sealed bottle: Glass bottles are preferable to plastic bottles because plastic is not completely gastight. water may be separated from the sample if it is left to stand for a long time.e. such as butter. you must be extremely careful to exclude atmospheric moisture . In such cases. which cannot be mixed as thoroughly as liquids. Heterogeneous water distribution in samples: In non-polar liquids. rinse the bottles two or three times with the sample beforehand. the water is not uniformly dispersed. Substances with very low water content: Substances with a very low water content are frequently extremely hygroscopic. it must contain the same average amount of water as the material as a whole.the most common source of error. In the case of non-polar solids. oils. you should take into account the following points: 1. This can happen when a sample cools and the water solubility is decreased. If the water content of a sample changes during sampling due to moisture being absorbed or desorbed. Use bottles with a septum stopper for liquids of very low water content. Hygroscopic solids may exhibit higher water content on the surface than inside if they have absorbed atmospheric moisture during storage. With liquid samples. the lower the amount of moisture. 5. 39 . The sample must therefore be taken very quickly and with a syringe or a spatula that is absolutely dry. or at least minimize. 4. The sample should be taken quickly to exclude. the absorption or release of moisture. If you have to store the sample. 2. Use a bottle with an optimum volume for the amount of sample: the smaller the gas space above the sample. e.1 Taking the sample When taking samples for water determination. 5. It floats on the surface or sinks to the bottom. the solubility of water in the sample can be increased using a solubility promotion agent such as 2-propanol.2 Storing the sample After you have taken the sample. "An analysis cannot be better than the actual sample!" When sampling. Liquids of this type must be thoroughly mixed (by shaking) before a sample is taken.

1 1. and the required accuracy and precision. the accuracy is improved if larger sample amounts are used.0 1000 1 1. because the absorption of air moisture during sampling and sample addition becomes less important. 10-50 μg water can be detected if the demand for repeatability is not too high. For coulometric analyses.4 500 2 1. a KF titrant with a lower concentration (1 or 2 mg/mL) has to be used.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5. If a high level of accuracy is required.2 1. Under optimum measurement conditions.01 10 8 0.25 100 4 0. Water content determinations below 1000 ppm are not required to be quite as accurate: a relative standard deviation srel of 1 to 5% is generally considered as acceptable for such values.5 to 17. the optimum amount of water is approximately 10 mg per sample. This corresponds to 0. sample size [ppm] [g] 10 8 50 7 100 5 200 4 500 3 1000 2 40 .0 For volumetric titrations.05 mL is thus still acceptable when using a 5 mL burette.1 to 0. approx. and the following minimum sample sizes should be used: Water content Min.0 5000 0.05 mg water per sample with a titrant concentration of 1 mg/mL. sample size Amount of water [ppm] [g] [mg] 1 10 0.1 mg water per sample. because the absorption of atmospheric moisture during sampling or sample addition becomes less important. the optimum amount of water is in the range from 0.3 Amount of sample The amount of sample used depends on • • the expected water content.5 mg water per sample for a 5 mL burette with a titrant concentration of 5 mg/mL. it is recommended to use the minimum sample size given in the following table: Water content Min. Repeatable results can be obtained even with 0.08 50 5 0. the amount of sample should require a titrant consumption between 30 and 70% of the nominal burette volume.1 to 0. In general. For a more accurate determination of water traces (10 ppm to 1000 ppm) by volumetric KF ttiration. the accuracy increases with the amount of sample. As a rule of thumb. For optimum accuracy with determinations in the range from 1 ppm to 1% water.5 to 2 mg water per sample.0 10000 = 1% 0. A titrant consumption of 0. This corresponds to 7.

The intersection point of this line with the "Amount of sample" scale represents the recommended amount of sample to be used. 1 mg for coulometric KF) or the recommended range The optimum point is connected by a straight line to the expected water content. Logarithmic scale! 41 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Determination of the amount of sample for a water content in the range from 1000 ppm to 100% Principle: The recommended sample size can be determined as a function of the expected water content for optimum KF analysis. Procedure: • • • Note: Start from the optimum point (10 mg for volumetric KF.

an optimum sample weight range is recommended. 42 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Example: Expected water content: Optimum amount of water: Optimum sample amount: 5000 ppm 10 mg/sample 2g The Compact volumetric and colometric KF titrators support the user with a sample size calculation routine. which is accessible in the online titrations screen: Dependent on the expected water content.

toluene. creams. honey a Waxy candle wax. 43 . suppositories b c Liquefy the sample in an oven at approx. Store the sample in a bottle with a septum stopper to avoid moisture absorption from the air. Rinse a 10 mL syringe 2-3 times with the sample Inject the sample using a 1 mL or 10 mL syringe through a septum cap. alcoholic beverages methanol. hydraulic oils. The syringe is heated together with the wax. yoghurt. you must take suitable precautions to prevent atmospheric moisture from being absorbed. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. Fill the 5 or 10 mL syringe with sample after removal of the piston.1 Liquid samples When adding liquid samples. aqueous emulsions. This prevents the sample from solidifying in the syringe during the weighing. ski wax. edible oils hexane. benzene glycerol.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6 Sample addition 6. especially with samples of low water content. In the case of a volumetric Karl Fischer titrator. silicone oil. paraffin. In the case of a volumetric Karl Fischer titrator. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. mineral oils massage oil Procedure Inject the sample into the titration vessel either through a septum (KF coulometer) or through the needle hole in the three-hole adapter (volumetric KF titrator) using a 1 mL syringe with needle. 50 °C and fill it into a syringe. Inject it into the cell using a wide-bore needle. Low water content Low water content Hygroscopic Viscous Very viscous ointments. Possibly warm the sample slightly to lower the viscosity. The following procedures are suitable for the different types of liquid samples: Sample characteristics High water content Low viscosity Examples perfumes. Inject the sample using a 5 or 10 mL syringe with a thick needle into the titration cell.

Sample addition of liquids with the back weighing technique – Fill the syringe to a quarter with sample. Fill a syringe without a plunger with molecular sieves. Fill the syringe with sample and wipe the needle with a paper tissue. use bottles with a septum stopper and pressure equalization. Replace the syringe with the remaining sample on the balance and back weigh it. a vacuum develops in the bottle with septum stopper and it will no longer be possible to take a sample aliquot. you must aerate the bottle with dry air (equalize the pressure). Empty the syringe (into the waste bottle) and repeat the rinsing two or three times.METTLER TOLEDO Good Titration PracticeTM in KF Titration Taking samples from a bottle with septum stopper After several samples have been taken. Air flows through the molecular sieve into the bottle when you take a sample aliquot. Withdraw the plunger so that the drop at the tip of the needle is sucked back into the needle. Otherwise when the syringe is removed. Enter the sample size in the titrator or transfer it automatically. To avoid this. Place the syringe (upside down) in a beaker on the balance pan and tare the balance to "0". seal it with cotton wool and insert it into the septum bottle using a short needle. If the sample is hygroscopic or has a low water content (< 1000 ppm). Start the titration. Start the titration method by pressing the <Start> button Inject the sample into the titration cell through the septum stopper. – – – – – – – – – – 44 . the drop will adhere to the septum. Withdraw the plunger and rinse the syringe with the sample by shaking it.

With an optimum sample size of 1 mg water/sample. crystalline samples: Weighing boat – Grind hard. Hard. fatty e. The sample should be quickly weighed and added to minimize air exposure.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6.g. about 50-100 μg water enter the anode compartment. For this reason. solid fat: – Grate the product and add the sample with a spatula.when the titration cell is opened to add the sample. the storage of samples in a refrigerator may cause water to condense. pulverize less hard samples in a mortar. Finely powdered Dusty Finely powdered with very low water content Soft – Use a weighing boat with an attached flexible tubing to add the sample: it prevents the sample from adhering to the wall of the titration vessel or to the electrode. jelly bears. 45 .g. cooled analytical mill. If possible. almond paste: Cut into small pieces with scissors or a knife and add the sample with a spatula. salicylic acid. e. it is necessary to warm up such samples to room temperature in a closed vessel before weighing. it should be added under the same conditions as it was transported and stored. Sample characteristic Brittle Hard/soft Pourable Procedure e. salts.g. jellied fruits. cellulose powder: – Either weigh the sample in a dry box or extract it externally. For instance. thus. – Add the sample with a weighing boat.g. other methods have to be used for the determination of low water content by KF coulometry in solid samples: • • • External extraction External dissolution Drying oven On the other hand. in a volumetric KF titrator solids can be directly transferred into the titration vessel. depending on the ambient humidity. this would lead to an error of 5% to 10%. coarse-grained samples in a closed.2 Solid samples It is not possible to directly titrate solid samples using KF coulometry . e. chocolate.

g. edible fat: – Homogenize the sample well: the water is heterogeneously distributed. Use a weighing boat with attached flexible tubing if necessary.g. margarine. The water content is often lower atthe surface than inside the sample. This prevents the sample from hardening inside the syringe during the weighing process Creamy Highly viscous e. The syringe is heated up together with the wax. Add the sample into the titration vessel. honey. because the water is released if it is pressurized Waxy e. – Add the sample with a spatula. candles. inhomogeneous e. Weight of solid samples with the back-weighing technique Weigh the sample in the weighing boat.METTLER TOLEDO Good Titration PracticeTM in KF Titration Soft. Start the titration. Tare the balance to zero. sugar products – The METTLER TOLEDO Visco-Spoon™ simplifies the handling with creamy samples since it can be directly mounted into the titration stand. ski wax. - 46 . Back-weigh the empty weighing boat. chocolate cream. 50 °C and fill them into a syringe. suppositories: – Liquefy the samples in a drying oven at approx. paraffin. Do not use a syringe. fatty.g. to prevent the sample from adhering to the vessel wall or to the electrode. Enter the weight in the titrator or transfer it automatically. butter.

g. cheese: Hard. almond paste (“marzipan”): Cut into small pieces with scissors or a knife. e. brittle Moderately hard. grain. noodles.g. hard salts: Grind in a closed.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7 Release of water from the sample Karl Fischer titration is only possible if the water in the samples is freely available. Sample preparation Water: Example: Biological samples First of all. dried fruit and vegetables.g.g.g. meat. crystalline products: Pulverize in a mortar. e.g.g. sausage. This is not the case with solids if the water is bound as. then reduce it further with a homogenizer in an external solvent. e. organic salts. in plants) Water Example: Sugar. e. Fibrous natural products Suspensions 47 . e. vegetable juices: Reduce with a homogenizer. chocolate. suitable sample preparations and special Karl Fischer methods are necessary to release water in these samples. berries: Reduce with a homogenizer in an external solvent. cooled analytical mill. it is necessary to crush insoluble solids in order to gain access to the trapped water. solid fat: Grate the product. e. fatty Mince the product. pharmaceuticals Water Example: Food Example: Gypsum (Ca2SO4 * 2 H2O) Thus. inorganic salts. coffee beans: Crush in a mixer.g.g. e.g. fatty Soft. e. brittle Viscous Hard. water adsorbed on surface capillary bounded water (e.: • • • • entrapped water water of crystallization (salts). jellied fruits. minerals. The following methods are available: Sample characteristic Very hard Procedure e. fruit juice extracts.

8 1.1 mg/pc 3. grinding the sample additionally with a built-in homogenizer (see photos below).2 1. Water is then extracted providing the mixing time defined in the titration method is sufficiently long.8 1. the homogenizer eliminates the need to use auxiliary reagents such as formamide with.0 1.1 1.8 4.1 4.3 1. You can speed up the extraction of water from the sample by • • In many cases.9 0. e.0 7.1 Internal extraction Internal extraction is suitable for insoluble solids that release water quickly when crushed: – – Add the crushed samples into the titration vessel.9 0. using either methanol or a mixture of it as the solvent.g.5 8. potato chips. hazelnuts.4 1.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.4 0.8 Solvent Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol 48 .9 srel / % 0. sugar.3 2. Thermostatable vessel High–speed homogenizer Examples: Sample Flour Potato chips Ground hazelnuts Chocolate Instant coffee Dried chives Dried tarragon Aspirin Sweetener tablets Optical bleaching agent Result / % 12. etc.4 1.5 1. heating the solution with a thermostating titration beaker.

the finely crushed sample is added to a solvent with very low water content and is left to stand until the water has been released from the sample. Briefly. In particular. Pay attention to the water capacity of chloroform (max. shaking bath) placing the solution in an ultrasonic bath for a certain time or reducing the sample further with a built-in homogenizer. 600 ppm).2 External extraction External extraction is suitable for insoluble solids that release water only slowly when crushed as well as for samples with an extremely inhomogeneous water distribution. curry) for dehydrated products for sugar (total water). methanol decanol / octanol formamide for insoluble organic solids for fatty and dairy products (butter. pepper.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. edible fat) for natural substances (almonds. Provide sufficient solvent for the blank value determination so that enough solvent is available for the extraction. 49 . butter milk. water is extracted from the sample by means of a defined quantity of solvent of known water content. 350 ppm) and toluene (max. sugar and starch products for sugar (surface water) The organic solvents most commonly used are: • chloroform The external extraction is carried out in four steps: Step 1: Blank value determination of the extraction solvent Solvent in septum bottle Take a solvent aliquot Water content determination of solvent = blank value B - The water content of the solvent must be much less than the one of the sample. The extraction of water can be improved • • • by shaking the solution (mechanical shaker.

or use a homogenizer. - 50 . the smaller the relative error because the total error is calculated with respect to the sample size. the addition of dry quartz sand has proven useful for improving and speeding up the extraction.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 2: Weigh in solvent and sample Weigh solvent in = msolv Add sample Weigh sample = mext - Cut the sample into small pieces so that it releases its water more quickly and efficiently. For the extraction of tablets. A dilution factor of 10 . Shaking is the method generally used for extraction. Step 3: Extraction - Shake.20 is normally used. A mechanical shaker is normally used because the extraction time is often long (at least two hours or overnight). Add a sufficient amount of sample. The larger the sample. or use an ultrasonic bath with heating.

1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m . 51 . take an aliquot and titrate Allow to settle Take an aliquot of the extraction solution Titrate sample The following equations are used to calculate the water content of the extracted sample: ⎛ msol B ⋅ msol ⋅ ⎜C ⋅ − ⎜ mext mext ⎝ ⎞ ⎟ ⎟ ⎠ For % : R (%) = 100 100 − C For ppm : 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − R( ppm) = 6 ⎟ mext ⎠ 10 − C ⎝ mext Water content in the sample P (% or ppm). R: C: B: msol: mext: m: Note: Blank value (water content of the solvent. Amount of solvent (g) Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) The detailed calculations which lead to these formulas are given in the appendix. % or ppm). Water content of the supernatant extraction solvent (% or ppm) %: C = (VEQ*CONC-TIME*DRIFT/1000)*0.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 4: Allow settling.

3 0. the weight of the sample (mext) and the weight of the aliquot of the supernatant solution containing the extracted water (sample size m) is entered into the respective sample data fields: 52 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Examples for the external extraction: KF Coulometry Sample Result / ppm srel / % Extraction solvent Sucrose (surface water) 72 4.5 Decanol:formamide:methanol 8:2:1 Decanol:formamide:methanol 8:2:1 Decanol:formamide 1:1 Decanol:formamide:methanol 8:2:1 Methanol Methanol Formamide There is a dedicated KF method type ‘External Extraction’.5 9. The weight of the solvent (msol). The METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator are available with optimized method parameters for immediate execution.4 4.2 Chloroform Volumetric KF Titration Sample Result / % srel / % Extraction solvent Cheese Liver sausage Mustard Chicken broth Tobacco Wool Acrylic paint 27. The solvent blank is determined directly from the method running in standby by pressing the ‘Start blank’ button.4 0.6 61.8 54.6 0.3 0.6 72.4 0.9 11.4 0.5 0.

“External extraction”) in the method function “Calculation”. for instance. The water content of the solvent should be as low as possible. In particular.e. the formula is automatically given. reaches the saturation limit for water already at 350 ppm! 53 . in order to maximize the extraction effect and ensure that the difference between the water contents before and after extraction is as large as possible. Note: 1. Chloroform. The amount of sample should be sufficiently large to ensure that the amount of water in the sample is significantly greater than that in the solvent prior to extraction. 2. The amount of sample should also take account of the absorption capacity of the solvent.METTLER TOLEDO Good Titration PracticeTM in KF Titration The equation for the calculation of the water content of the extracted sample is predefined in the calculation method function. 3. by selecting the appropriate calculation (i.

waxes and suppositories Example: Sample Result / ppm srel / % External solvent Sucrose (total water) Naphthalene Phenol Salicylic acid Contact adhesive (“Rubber cement”) 533 35 174 116 278 4.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % AND ppm: R: C: Water content in the sample P (% or ppm) Total water content (sample + solvent).1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m B: msol: mext: m: Blank value (water content in % or ppm) of the solvent.3 External dissolution External dissolution is defined as the complete dissolution of a sample in a defined amount of solvent of known water content.2 10. The following solvents are commonly used: • • • • methanol formamide chloroform toluene for organic solids for sugar products for petroleum oils and adhesives for tar.2 1.3 formamide methanol methanol methanol chloroform The method corresponds to external extraction except that the sample dissolves completely in the external solvent. External dissolution is suitable for soluble solids with an extremely inhomogeneous water distribution. ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%. only the calculation method function has to be adapted to by selecting the corresponding calculation from the list of proposed results. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) 54 .9 5. or with a very low water content.8 2. %: C = (VEQ*CONC-TIME*DRIFT/1000)*0. The dedicated method type ‘External Extraction’ and the METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator can be used as templates. or with a high water content Pure solvents can be used to dissolve the samples. the addition of methanol is not necessary. in % or ppm.

KF coulometry is not suitable for samples with water contents of 10-100% because a very small amount of sample would have to be used. foodstuffs) in septum bottles means that external extraction or external dissolution as described in the previous sections are not recommended. 55 . If the solid has a low water content (<200 ppm). and too much titrant is consumed.20 mL of anolyte titrated to dryness into the syringe. 3. Determine the weight of anolyte injected by back weighing. because a large sample amount leads to a too long titration time. In fact. 7. On the other hand. Thus. Direct titration is not suitable.METTLER TOLEDO Good Titration PracticeTM in KF Titration To obtain accurate results a large sample amount is used for substances with an inhomogeneous water distribution. 7.g. Rinse the syringe two or three times in this way. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. the sample is previously diluted through external dissolution to be able to titrate a larger sample aliquot. serum. Draw an aliquot into the same syringe again. weigh it and inject it into the titration cell. 4. the blank value correction is too large compared to the amount of water in the sample. If 1 g of sample has a water content of 100 ppm (= 100 µg) for instance.4 Lyophilized substance in septum bottles The extremely low water content of freeze-dried substances (e. the error as a result of opening the titration stand will be between 10 and 30 µg. Determine the weight by back weighing. biological tissue. Remove approx. the error obtained by direct titration if the titration stand is opened to add the sample is too large. 2. Since you are able to work with larger amounts of sample when working with this technique. You should therefore proceed as it follows: Take an aliquot of anolyte Inject it in the septum bottle Shake Take aliquot and titrate Procedure: 1. 5. this error is reduced. Draw 10 . 6. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. weigh it and inject it into the septum bottle.

The water amount in µg is determined. Draw exactly 20 mL of anolyte titrated to dryness into the syringe and inject it into the septum bottle. 4. Alternative procedure: 1. neither the calculation for the external extraction nor for the external dissolution are needed for this procedure using the volume instead of the mass. 5. Draw exactly 5 mL from the septum bottle into the same syringe again and inject it into the titration cell. 2. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. 8. 7. Since ¼ of the total amount was injected. zero must be entered for the blank value (B). With a standard method calculation and calculate the water amount in µg. In this way. Thus. 3. The accuracy of a plastic syringe is enough. the final result must be multiplied by 4 (factor f = 4). 6. the water amount in the septum bottle is 4 times larger. then you can additionally calculate the result can be given in ppm.METTLER TOLEDO Good Titration PracticeTM in KF Titration If the sample is completely dissolved: use the method type “External extraction” and the calculation for the "External dissolution" If a suspension is formed: use the method type “External Extraction” and the calculation for the "External extraction" Note: In both cases. Rinse the syringe two or three times in this way. Remove approx. If you know the lyophilized sample amount in the septum bottle. because the anolyte titrated to dryness has a blank value of "0". 56 .

Calculate the volume from the time and the gas flow rate. The gas must be directed through a water-dissolving. hydrochloric acid. start the titration and reset the three-way valve to its original position in order to direct the gas into the titration vessel.g.As soon as the drift is stable again.Purge the system with the gas before you start the determination. depending on the water content of the gas. 600 s as termination parameters. evaporated methanol lost in the gas stream must be replaced depending on titration time and number of determinations. . . .Adjust the gas stream to a constant flow rate with the control valve: 50 to 200 mL/min. Three-way valve Flow meter Gas Control valve The flow rate has to be constant to determine the volume necessary to calculate the water content: gas volume = gas flow rate x time. .METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. Notes .g. to prevent the gas from flowing into the titration vessel. The water contained in the gas is then absorbed by the liquid and can be determined by means of Karl Fischer titration in a process similar to external extraction. Sampling/sample addition . you should titrate the gas sample directly from the source.Purge the sample vessel and the tubings thoroughly beforehand with the gas. 57 .Add a sufficient amount of buffer solution into the titration vessel to determine the water content of acid gases such as e.With sample vessels the gas amount gas can be determined by differential weighing.Turn the three-way valve.When titrating large quantities of gas in the same solvent. . . the gas must be directed through the titration vessel for a defined period of time. water-free absorption liquid in which CO2 itself does not dissolve. you must fill the gas either into special gas sample tubes or into small steel cylinders. time" and a "Delay time" of e. .If possible.Select "Max.CO2 gas can not be titrated directly since iodine reacts with CO2. . . to ensure that the titration is terminated after the maximum time.Stop the gas flow after 1 to 2 mL titrant has been consumed. . The water content in ppm is calculated by entering the volume and the density. Determination . If not.5 Determination of water in gases To determine the water content of gases.

the oven temperature should not exceed 160 °C. Experiments with various gas flow rates yielded the following results: Gas flow rate Recovery [mL/min]: [%]: 108 99. 7. causing the water in the sample to vaporize.1 - The recovery rate is clearly decreasing with increasing gas flow rate.0 mg/L Therefore.6. that release water very slowly.2 Purge gas Air contains oxygen. For Karl Fischer titration.6. you should use a two-stage pressure regulator so that the final pressure is in the range 0.5 .5). 58 . cause side reactions with the Karl Fischer reagent.7 500 97.9 166 99. 7. cf. If you use nitrogen from a gas cylinder. which could react with the sample at higher temperatures. the residual moisture in the purge gas should be less than at least 10 μg/L (for coulometric determination) and 20 μg/L (for volumetric KF titration) in order to obtain accurate and repeatable results.: o o air with 50% humidity: approx. Thus. Air should therefore only be used for non-oxidizable.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.6. e.1 bar (cf. for accurate results do not select a too high gas flow rate. The purge gases commonly used contain moisture. chapter 7.4 – 8. inorganic samples. and the amount of water is determined.6 Determination using the drying oven This method is suitable for solids and liquids that 1. 150 mL/min is ideal for DO308 and 70 mL/min for Stromboli (automated KF drying oven. chapter 7. The water is transferred to the titration cell in a current of dry inert gas (purge gas). or 2.g. the purge gases must be first dried before entering the KF oven.1 Principle The sample is heated in an oven. If you use air for organic samples. 11 mg/L nitrogen gas from a cylinder: 1.6.4) A gas stream of approx.

Silica gel can be regenerated over night at 150 °C.e.3 Procedure There are two different methods to perform a KF titration with the drying oven: 1.80 µg H2O/L 40 . Passing the gas stream into the titration cell causes the anolyte (in the KF coulometer) and solvent (generally methanol in KF volumetric titrator) to vaporize. The short mix time is necessary so that a delayed vaporization of water does not lead to premature termination of the titration. you should set the maximum titration time as the termination parameter (i.60 s). With some samples the drift at the end of the titration is significantly higher than the initial drift. Method 1: The water evolved is continuously titrated After a short mix time (20 .e. all the water is vaporized and transferred to the titration cell.6. especially methanol. in contrast to other desiccants. Silica gel is appreciably better in this respect.METTLER TOLEDO Good Titration PracticeTM in KF Titration Several agents are available to dry the purge gas: Method Residual moisture Residual moisture for 200 mL/min gas flow rate (drift) Sulfuric acid. deactivate the drift stop). The amount depends on the gas flow rate and the type of KF reagent present in the titration cell.50 µg H2O/L 15 – 20 µg H2O/L 50 – 60 µg H2O/L 5 – 10 µg H2O/L 10 – 15 µg H2O/min 8 – 10 µg H2O/min 3 – 4 µg H2O/min 10 – 12 µg H2O/min 1 – 2 µg H2O/min You can use the following desiccants to dry the purge gas: – – Molecular sieves are the best drying agent as far as residual moisture is concerned. In such cases you should use the maximum titration time as termination parameter (i. In order to avoid the latter you may also use the minimum time as termination parameter. The relative drift stop or the maximum titration time can be used as the termination criterion. To ensure that the determination is repeatable. the titration starts and the released water is continuously titrated. At the end of the titration. whereas molecular sieves requires temperatures up to 300 °C. This is caused by a slow release of the final traces of water or slow thermal decomposition of the sample. there are two types of anolyte solutions: 59 . P2O5 KF one-component reagent Silica gel Molecular sieves 3 Å 50 . deactivate the drift stop). they are rapidly exhausted. The KF titration is then started. 100% Phosphorous pentoxide. 7. the vaporization is often very irregular. Silica gel and molecular sieves have the advantage that they can be regenerated. but their water absorption capacity is low. Method 2: The water is first vaporized and then titrated afterward During a defined long mix time. i. In the case of KF coulometers. 2. It is therefore recommended to dry the gas with a combination of silica gel and molecular sieves. Start off with the silica gel to absorb the bulk of the water and then use molecular sieves to reduce the residual moisture to a minimum.e.

time Max. Due to the vaporization of the methanol. oven temperature 200 °C: approx. time 60 . fibers) or with samples of low water content.2 99. the faster the water is titrated.5 mL/hour Anolyte containing ethylene glycol.8 6.7 99.9 2. oven temperature 200 °C: approx. Coulomat AG Oven): Anolyte loss at 150 . Make sure that the level of the anolyte does not fall below that of the catholyte (higher drift!).g.95 98.5 .2 1. 7. This is particularly important with low-weight samples (e. As an example data from coulometric determinations are indicated here below: Method Anolyte Gas flow rate Recovery / % 1 1 2 2 Coulomat AG Coulomat AG Oven Coulomat AG Coulomat AG Oven 166 mL/min 183 mL/min 166 mL/min 106 mL/min 99. The procedure for the determination of water content is described in the operating instructions.g.e. An air pump is available as an optional accessory. time Max.g. The DO308 oven is equipped with a gas drying unit with two bottles for silica gel and molecular sieve.METTLER TOLEDO Good Titration PracticeTM in KF Titration – Standard anolyte solutions containing methanol (e.4 Manual Karl Fischer drying oven The METTLER TOLEDO DO308 drying oven can be operated in a temperature range from 50 to 300 °C. time Max.200 mL/min. 3. i. and the better the recovery. as well as a gas flow meter.2 4.6. It has a large glass sample boat capable of holding up to 10 cm3 of sample.5 190 280 140 300 300 200 15 10 15 20 10 15 Max. there is a small loss of water.9 9. Coulomat AG or CombiCoulomat frit): Anolyte loss at 150 . The recovery therefore depends on the amount of methanol vaporized and the method used. you should replace the anolyte lost through vaporization with new anhydrous methanol. of samples srel / % T /°C Time/min Comments Polyamide Polyethylene Motor oil Cement Cooking salt Carbon black 5547 68 842 8200 360 3583 6 6 6 6 5 5 0. time Max. i.1 Briefly: The less methanol is vaporized. dedicated anolyte to be used with a KF Oven (e.e.200 mL/min. time Max. 1 mL/hour – From time to time. the recovery is not 100%.4. Examples: Sample Result / ppm No.

purge the "cold zone". 10. replace the silica gel and molecular sieves of the gas drying unit. and/or replace the anolyte of the KF coulometer. the evaporated solvent lost in the gas stream has to be replaced. Some samples require some time before water starts evaporating. and does not drop into the cathode compartment/ titration cell. This leads to a too low result.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments: 1. Close the stop cock and purge the "hot zone". 6. in volumetric KF titration the methanol loss is approx. you should proceed as follows: 7. evaporated solvent does not condense in the drying tube. . Set a gas flow rate of 150-200 mL/min. The evaporation is reduced by adding ethylene glycol (higher boiling point) to a maximum solvent ratio of 20-30%. Coulometer KF: The internal drying tube of the generator electrode has to be replaced with an external. Add the sample through the tapered joint and slide the glass boat with the sample into the oven: Guide rod with magnet Slider Glass sample boat 8. 61 9. do not select the parameter "Auto start". In such cases. The drift should be 5-10 μg H2O/min at a gas flow of 150 mL/min. 2. For instance. the recovery increases to 99. you may use the SIGMAALDRICH HYDRANAL® water standard KF oven 5.55% or VWR/VWR/MERCK water standard KF oven 1%. Then. 3. 4. 5. This can happen when the titration is started only after complete evaporation. Open the stop cock. For the same reason. To check the performance of the titrator/drying oven system. If the drift is higher than 15 μg H2O/min. Experiments using methanol as the solvent gave a recovery rate of 98% for a stream of 166 mL/min. A large amount of evaporated water cannot be fully absorbed by the solvent. If several determinations are performed in the same solvent. bent drying tube. Here a short mixing time (15 to 60 s) or the minimum titration time should be defined to prevent the titration from being terminated too early. start the titration so that the drift value is automatically entered. 3. If the drift is constant. Some samples have surface water that is lost as soon as the oven is purged with dry gas.5 to 4 mL/h for an oven temperature of 200 °C and a flow rate of 200 mL/min. Always start the titration before you place the sample in the oven to ensure that the correct drift value is adopted by the method (online drift).7%. If the water is titrated as soon as it begins to evaporate.

STROMBOLI offers one fixed place on the sample rack for an empty sample vials in order to determine the drift value. The sample vials are moved upward into the oven by a lift. 62 . The blue rubber cap seals the sample vial tightly against the oven. After the analysis.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. Besides 14 places for glass sample vials. The drying oven can be operated in the temperature range from 50 to 300°C. 3. are included in the titration method. 2. while a glass tube pierces the aluminum foil cover. including the oven temperature. the lift is moved downward and gravity facilitates the removal of the sample vial from the oven. The purge gas flows through the sample vial and the water vaporized is transported via the transfer tube into the titration cell of the coulometer. STROMBOLI is completely controlled by the titrator: all the parameters for the determination. The oven heats the sample to the set temperature. 1 During a sample series: 2 3 1.5 STROMBOLI automatic oven sample changer The METTLER TOLEDO STROMBOLI oven sample changer is a drying oven for automatic Karl Fischer titration with the KF Compact Volumetric V30 and Coulometric Tititrators C30 as well as with the Titration Excellence Titrators T70 and T90.6.

To determine the drift value accurately. This is particularly important with light samples (e.g. The drift value is defined as the moisture entered into the titration cell by the purge gas. fibers) or with samples of low water content. The sample vials are sealed with self-sealing aluminum foil and a rubber cup. This takes 10-20 minutes as can be seen in the following diagram: 63 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Sample vials: Rubber cap Aluminum foil Sample vial The glass sample vials have a large volume (up to 25 mL). Drift determination: The drift determination is performed with an empty vial on the first position of the sample rack. the moisture in the empty sample vial has first to be removed.

g. the blank value determination also takes the actual drift into account. a blank value determination should be performed before each series of samples since the ambient conditions (humidity. the moisture in the air present in the vial. drift value x time). In this case. In the same way. The blank value should be determined before each series because the humidity can change. and thus the moisture adsorbed on the glass walls is not always the same.e. i. Nevertheless. In this case. The loops run through one after the other and the samples are processed sample for sample. The first sample of the next loop is then transferred into the oven and the water determination begins. you can enter the number of samples the series includes for each loop. With rapidly changing. At the start of the method. the moisture content is somewhat lower.300 μg water. they can be measured at different temperatures using the same method. a blank determination can be performed between two sample loops. the drift value can change with time. the silica gel and molecular sieves in the bottles of the gas drying unit can be replaced. the last sample vial that was baked out remains in the oven until the temperature has stabilized at the temperature of the next loop and the drift is low and stable. different plastic samples have to be analyzed. a drift determination should still be performed at least once a day in order to check whether the drift is too high (e.e. Thus.e. To determine the blank value as accurately as possible. and the adsorbed moisture on the glass walls of the vial) minus the amount of water due to the drift (i. you can check whether the drift is constant and the new drift value can be used for the next series. If. gas flow. 64 . one with the same properties as the sample vials into which the samples have been filled in). Performing the drift and blank value determination In general. Multiple sample series at different temperatures Several series can be started on the same sample turntable – even at different temperatures. at the end of a series the blank value can be measured again and compared with the value determined at the beginning. moisture in the sample vial.e. If the maximum titration time is used as termination criterion in the method -which is what we recommend. it is important to use a new sample vial for each blank value determination (i. For each series. for example. The new blank value is automatically used for the blank correction. suboptimum conditions. If the temperatures of successive loops are different. Important: After a blank value determination. the vial used no longer has the same properties as the "fresh" sample vials. These method templates are based on a dedicated KF method type called ‘Stromboli’. This means that the stored drift value of the previous determination will be used. If this is the case. It is therefore not necessary to perform a drift determination before each series. as well as the anolyte in a coulometric analysis. several blank value determinations can be performed one after the other in the same loop and the mean value calculated from the results. There are dedicated METTLER TOLEDO multi-loop methods available in the V30 (M313) and in the C30 (M396).the analysis times for the determination of the blank value and for each sample are the same. > 15 μg H2O/min). the method contains a so-called sample loop. The optimum blank value is in the range of 70 . whose optimum bake-out temperatures differ. The blank value can also vary as a function of temperature. By performing a drift determination at the end of the series or between several series. etc.METTLER TOLEDO Good Titration PracticeTM in KF Titration Blank value determination: The blank value is the amount of water contained in an empty sample vial (i.) are always slightly different.

5. Use the same vials for a sample series as well as for the blank value determination.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments on the operation with the STROMBOLI oven sample changer: 1. bent drying tube.55% or VWR/VWR/MERCK water standard KF oven 1%. To check the titrator/drying oven system. see also list of results). This has a large effect on the blank value and thus on the result. drying and storage). The delivery tube has a T-piece that causes a small leak flow.g. Vials that have undergone different treatment can show differences in the blank value of 50-150 μg water. A sudden shutdown of power immediately switches the valve in that way. that the inert gas stream to the gas source is closed and the system is ventilated with ambient air. toluene. This is necessary so that the KF solvent or anolyte is not aspirated into the hot sample vial if Stromboli is not properly shut down while it is still hot. An optional 3/2 way valve which is automatically controlled by STROMBOLI can be used instead of the T-piece mentioned in 1. The amount of moisture adhering to the glass surface of the sample vials strongly depends on how the vials were treated beforehand (cleaning. 8. Allow sample vials that have been used or cleaned to stand overnight in the atmosphere for conditioning before starting measurements. With STROMBOLI. you can use SIGMA-ALDRICH HYDRANAL® water standard KF oven 5. These are partially vaporized (e. This test also serves to check the tightness of the oven and the connection tubing 65 . This valve shall be used especially if inert gas sources are used. 7. evaporated solvent is not condensing in the drying tube. since it provides a leak free inert gas stream during normal operation. 3. and therefore it does not drop into the cathode compartment. motor oil) or completely vaporized (e.g. 4. Therefore no precious inert gas is lost and no vacuum is applied to the system which may result in a back aspiration of the anolyte into the hot oven. Set a gas flow of 40–60 mL/min. you can not only determine solids but also liquid samples. A special (longer) gas inlet glass tube is provided to bubble gas into the liquid. 2. 6. KF Coulometer C30: The internal drying tube of the generator electrode has to be replaced with an external. In this way.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

Examples:
Sample Result [ppm] No. of samples srel [%] T [°C]
Max.Time

[s]

Comments

Polylactic acid 0.5 g Polymer ABS-50 T 10014 3g Polymer ABS-50 F10014 2g Motor oil 1120/03 (AA) 2g

2589

3

1.1

160, air 190, N2gas 170, N2gas 165, air

--

Stir time: Max. time: rel. drift:

600 s 300 s 3 µg/min

736

5

1.1

300

Stir time: 900 s Delay time: 300 s Stir time: 900 s Delay time: 300 s Stir time: 60 s Delay time: 300 s Very slow evaporation, not faster with 180°C, above 180°C decomposition Stir time: 60 s Delay time: 300 s Very slow evaporation, above 180°C decomposition

1312

13

0.9

300

241 261

3 4

4.4 7.9

1500

Motor oil 1034/03 (AA) 1.5 g

426 438

4 3

2.7 4.5

180, air

1800

66

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

8 Measurement results
8.1 Resolution and detection limit
The following table indicates the theoretically smallest increments of current (KF coulometric) and titrant (Volumetric KF) which could be achieved by the instruments based on their technical specifications. Therefore, these are indicative values and they should be considered as such:
C20/C30 Compact Coulometric Instrument V20/V30 Compact Volumetric Titrator Resolution: 20’000 burette steps
5 mL burette: 0.25 µL c=5 mg H2O/mL: 1.25 µg H2O/step

Theoretical smallest increment

0.1 mC
Theoretical: Resolution:

(100 mA x 1 ms)
0.01 µg H2O < 0.1 µg H2O

Detection limit (limit of detection, LOD)

10 µg
Example: 10 g sample → determ. of 1 ppm Assumptions: - Current is used for iodine generation - Generated iodine is reacting 100% with water only.

50 x resolution
5 mL burette: 12.5 µL c=5 mg H2O/mL: 62.5 µg H2O Example: 5 g sample → determ. of 12.5 ppm

The theoretically smallest current increment that can be generated by the C20/C30 Compact Coulometers is 0.10712 mC which corresponds to 0.01 μg water. However, the achievable resolution of the instrument is in the order of less than 0.1 µg H2O, whereas the detection limit (also called “limit of detection”) is approx. 10 μg water per sample. Thus with a 10 g sample, 1 ppm water can be determined. For the V20/V30 Compact Volumetric instruments, the detection limit mainly depends on • • • The resolution of the burette drive, i.e. the max. number of steps which can be achieved by the stepper motor. the burette volume size; generally, a 5 mL burette is used for volumetric KF titration. The concentration of the titrant.

8.2 Measurement accuracy
The accuracy strongly depends not only on the technical specifications of the instruments, but also on the several factors that have been already mentioned in the previous chapters: 1. Sampling (including suitable storage, if necessary) 2. Sample treatment and preparation 3. Expected water content and selection of suitable instrument 4. Selection of optimum sample size 5. Condition of the KF reagents, i.e. fresh reagents, pre-titration, low drift value, … 6. Sealed titration vessel and tight tubing, 7. Condition of the indication electrode 8. Coulometry: condition of the generating cell 9. Parameter settings in the titration method etc. 67

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

To determine the closeness of agreement between the result of measurement and the true sample value, measurements can be performed either by titrating water standards or by titrating samples with known water content. The measurement accuracy depends on all the various factors described and explained in the previous sections. The crucial factors are optimum control as well as the water content and the amount of the sample.

8.3 Repeatability
The closeness of the agreement between the results of successive measurements of the same sample can be expressed quantitatively as the relative standard deviation, srel, given as %. With optimum sample amount and control, the following values can be obtained under test conditions for repeatability. The graph shows the relative standard deviation for different water contents. In general, the repeatability of a sample series becomes worse with decreasing water content. Note that for water content below 10 ppm it is not recommended to use a volumetric technique.

100% 10% 1% 1000 ppm 100 ppm 10 ppm 1 ppm

Coulometry
Not suitable for coulometry

Volumetry
srel < 0.5 %

srel < 0.5 %

srel 5 - 0.5 % srel 5 - 0.5 % srel > 5 % srel > 5 %
Not suitable for volumetry

In the following graphs, the relative standard deviation srel (%) of several series with different water content are given as a function of the sample size:

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5 1.0 3. Therefore.0 2.0 5.0 Sample size (g) In both cases. sample size for different water contents: KF Coulometry KF Volumetric Titration: srel (%) 6 110 ppm 5 330 ppm 4 720 ppm 3 2 1 0 0. A good repeatability is achieved the sample size is increased particularly for low water content values. it is necessary to use the optimum sample size in order to achieve precise results. with decreasing sample size the relative standard deviation srel becomes worse.25 0. 69 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Relative standard deviation srel vs.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

9 Interferences
9.1 Effects of temperature
Temperature effects on the KF titrant The Karl Fischer titrants consist of approximately 90% methanol or ethanol. Their volume increases considerably if the temperature increases, and their concentration decreases accordingly. S. Eberius [3] specifies a correction factor of 0.0012 per degree Celsius for methanolic Karl Fischer solutions. According to ISO 760, a temperature increase of 1 °C causes a drop of 0.1% in the concentration. The titrant (in particular, the two-component KF solvent) may loose sulfur dioxide if the temperature rises. This causes bubbles to form in the titrant tubing, an effect which is worse the faster the rate at which the burette is filled. These titrators allow you to define the filling rate of the burette separately for each titrant, e.g.:
Temperature / °C < 15 15 – 30 > 30

Filling rate for one-component KF volumetric titrant / % Filling rate for two-component KF volumetric titrant / %

100 80

100 60

70 40

Titration at low temperatures You can perform Karl Fischer titrations at low temperature to eliminate undesired side reactions. The water content of peroxides, for example, can be determined at -40 °C. You must use the two-component reagent to do so, because the reaction rate of the onecomponent reagent is too slow at this temperature. Titration at high temperatures Increasing the titration temperature speeds up the dissolution of the sample or the extraction of the water from it, resulting in shorter titration times. Titrations at elevated temperature have proved particularly effective for foodstuffs, e.g. sugar, flour, potato flakes, hazelnuts, custard powder. The maximum temperature depends on the boiling point of the reagent (boiling point of methanol: 64 °C, boiling point of ethanol: 78 °C).

9.2 Side reactions
Side reactions that falsify the results can occur parallel to the Karl Fischer titration. There are mainly three side reactions that can affect the result: 1. Reaction with methanol, CH3OH Aldehydes and ketones react with methanol leading to additional water Esterification with carboxylic acids leading to additional water Ketones and aldehydes react with sulphur dioxide, a base and water (i.e. water is consumed) The reaction of iodine with e.g. oxides, hydroxides, carbonates, amines, ascorbic acid, and mercaptans leads to a higher consumption of iodine giving higher water content.

2. Reaction with water, H2O

3. Reaction with iodine, I2 -

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Good Titration PracticeTM in KF Titration

9.2.1 Reaction with methanol
Aldehydes and ketones: Methanol, CH3OH, reacts with aldehydes (R-CHO) and ketones (R-CO-R) to form acetals (CH3-CH(OR2)2 , and (CH3)2C(OR2)2 respectively, the latter also called ketals), as well as water: Formation of acetals:

CH3CHO + 2 CH3OH
Formation of ketals:

→ →

CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O

(CH3)2CO + 2 CH3OH
Solution: -

Use the special reagents for aldehydes and ketones with these substances (so-called K-reagents). They contain other alcohols than methanol. - Experiments have shown that the side reaction still takes place despite these reagents. Each time acetone is determined, for example, the drift is higher than before the titration: the larger the sample, the greater the drift increase. It is therefore recommend to perform the determination with a small sample amount and to replace the solvent after two or three samples. Esterification: Methanol, CH3OH, reacts under presence of strong acids (i.e. sulfuric acid) with carboxylic acids (R-COOH) to an ester (R-O-CO-CH3) and additional water:

R-COOH + CH3OH →
Solution: -

R-COO-CH3 + H2O

First neutralize the sample using a suitable base (imidazole) before KF titration.

9.2.2 Reaction with water
Another side reaction, the bisulfite addition, occurs with aldehydes and ketones in the presence of SO2. Water is consumed in the process. Bisulfite addition:

CH3CHO + H2O + SO2 + NR R1-CO-R2 + HSO3Note: SO2 + H2O = HSO3- + H+ Solution:

→ →

HC(OH)SO3HNR R1(R2)C(OH)SO3-

- Start the titration immediately after adding the sample. - Perform a fast titration by predispensing 90% of titrant consumption This causes the water to be titrated quickly, before any bisulfite addition can take place. The "Autostart" parameter allows for the automatic start of the titration as soon as the sample has been added and water is detected.

9.3 Reaction with iodine
The Karl Fischer reaction is a REDOX reaction with iodine as the oxidizing agent. Thus, iodine may also react with readily oxidizable samples. On the other hand, iodine can also be reduced by SO2 in some samples such as e.g. oxides. Both reactions cause additional iodine being consumed, giving a false higher water content.

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Good Titration PracticeTM in KF Titration

The following substances can react with iodine:
Ascorbic acid Boric acid, H3BO3 Disulfite, S2O5 2– Hydroxide, OH– Mercaptans, R-SH Peroxide, R-O-O-R Sulfite, SO3 Tin(II) salts
2–

Arsenite, AsO2 – Tetraborate, B4O7 2– Iron(III) salts Hydrogencarbonate, HCO3– Nitrite, NO2
– 2– 2–

Arsenate, AsO4 3– Carbonate, CO3 2– Hydrazine, N2H4, and its derivatives Copper(I) salts Oxides, e.g. CaO, MgO, MnO2 Silanols, R3-Si-OH Thiosulfate, S2O3 2–

Selenite, SeO3 Tellurite, TeO3

Solution: The Karl Fischer titration for the majority of these substances can be performed with the aid of the drying oven, or also by performing an external extraction.

9.4 Example: reevaluation of side reactions
The water content obtained is too high if side reactions previously described have occurred. This can also be the case if a drying oven is used, and the sample slowly decomposes. Nevertheless, the correct result can be reevaluated by graphical extrapolation. Example: Water determination in red polypropylene fibers.
µg water

250 °C 160 °C 120 °C

300 200
115 mg 640 ppm

100

0

5

10

15

20 min

The determination was carried out for a period of 20 minutes (max. time) with the drying oven set to 120 °C, 160 °C and 250 °C. The following results were obtained:

120 °C 1186 ppm

160°C 1442 ppm

280°C 1955 ppm

The volume-time curve clearly indicates the occurrence of a side reaction, which becomes faster with increasing the temperature. The "water content" increases with temperature. By reevaluation using the LabX® titration PC software the actual water content can be obtained by extrapolating the titration curve to time t = 0 min (green dotted lines). The content is 115 mg water; this corresponds to a water content of 640 ppm for a sample weight of 0.18 g. The extrapolated result was confirmed by an external extraction in methanol. In fact, the result obtained with this method was 610 ppm.

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Clean titration cell and generator electrode and dry at 50 – 80 °C .Lengthen vaporization time (increase t max) . increase t(max) Wrong control parameters .Replace silica gel and molecular sieve in the gas drying unit The drift remains too high during standby titration Drift is too high after the titration of a sample Side reaction with the anolyte .Measurement electrode is faulty Titration stand not protected against moisture .Level of anolyte should be higher than that of the catholyte .Measurement electrode is not plugged in . Oven: . drift stop .Replace anolyte Amount of sample too small .Use t(max) as termination parameter .Check whether titration stand is completely tight.Increase amount of sample to ensure that approx.METTLER TOLEDO Good Titration PracticeTM in KF Titration 10 Troubleshooting 10.Increase value for rel. .Check whether titration stand is completely tight. Water distribution in the sample is not homogeneous .Clean the platinum pins of the measurement electrode with paper tissue .Replace molecular sieves and silica gel in drying tube .Increase end point Oven: water vaporizes very slowly and irregularly .Use higher oven temperature .Increase vaporization time.Homogenize sample. titration never ends Very long pretitration Poor repeatability Wet anolyte . . 1 mg water per sample is present.Higher oven temperature .g.Grease the tapered joints Moisture from cathode compartment and diaphragm .Use rel.Use smaller sample Long titration time.Replace anolyte .Add a small amount of one-component KF titrant to the catholyte.1 Coulometry Problem Possible causes and action to take Anolyte is not bright yellow but dark yellow to brown Drift is too high after the pretitration of a fresh anolyte .The repeatability is strongly dependent on suitable sample preparation and sample addition. especially at low water content (< 1000 ppm) 73 . . e.Use a different method Oven: water not completely vaporized . drift stop as termination parameter. if possible increase amount of sample Wrong sample preparation and sample addition .

bad repeatability With water standard 1.Too high value: see above “too high value” .Use back weighing.Lengthen vaporization time (increase t max) .Clean titration cell and measurement electrode Poor sample preparation and addition Samples of low water content (< 1000 ppm) are always hygroscopic.3 g Generator electrode is contaminated The black cover cannot be removed. Sample not dissolved (emulsion) .Check drift and blank value .Replace or change the anolyte .METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon .Use start cautious Oven: .Use higher oven temperature .Replace anolyte If this doesn’t help.0 or 0. It has no influence to the result.Sample not thermal stable: Use lower oven temperature . If the sample preparation and addition is not done carefully.Add chloroform or another solvent (maximum of 30%) to the anolyte to dissolve the sample Oven: . bad repeatability Platinum parts of the generator are colored black Warning: “Conductivity too low” 74 . 10 – 15 minutes .Add sample into KF reagents.Sample is oxidized: use nitrogen as a purge gas Checking coulometer Out of limits. do not splash to the walls of the cell.Too low value: see above “too low value” if this does not help.Replace anolyte . .Reduce the value for rel.1 mg/g . the Coulometer must be adjusted With water Standard KF Oven 1 %.2 . For samples with very low water content < 30 ppm .use a bigger sample size up to 0.Use fix generator current 100 mA . contamination with atmospheric moisture occurs.0. Checking drying oven Out of limits. drift stop . . check generator electrode.Use smaller sample size Values too high The titration was too fast → overtitration .Replace or repaire generator electrode. at 170 °C.Extend tmin (minimum titration time) Incomplete sample addition . Anolyte has too low conductifity . if it is defective.

titration never ends Wrong termination parameters .Shake titration vessel The drift remains too high during standby titration Titration stand not protected against moisture .Increase vaporization time.The repeatability is strongly dependent on suitable sample preparation and sample addition. drift stop" as a termination parameter.Extend tmax (maximum titration time) . e. external extraction. .METTLER TOLEDO Good Titration PracticeTM in KF Titration 10. . increase t(max) Long titration time.Use different method.Use longer mixing time or different solvents which dissolves the sample or extracts the water quicker. e.Increase value for relative drift stop. Low water content (<1000 ppm)! .Clean platinum pins of the electrode with a paper towel. if possible increase amount of sample. 75 .Increase amount of sample to ensure 10 mg water per sample. Titration stand not protected against moisture .Increase oven temperature .see above Oven: . drying oven. Oven: water is not completely vaporized .Extend vaporization time (increase t max) . etc.2 Volumetric Karl Fischer Titration Problem Possible causes and action to take Titrated solution is dark Drift too high after pretitration of fresh solvent Overtitration .g.Grease the tapered joints Condition Titration stand .Check and optimize control parameters. Side reaction of the sample with the KF reagent .Check whether titration stand is completely tight.g. Water distribution in the sample not homogeneous .Replace silica gel and molecular sieve in the gas drying unit Drift too high after titration of a sample The sample has not completely dissolved and continuously releases water .Replace molecular sieves and silica gel in drying tube . .Use t(max) as termination parameter .Homogenize sample.Use higher oven temperature .Use "Rel.Increase endpoint potential Oven: water vaporizes very slowly and irregularly .Reduce sample size Poor repeatability of the results Amount of sample too small . Wrong control parameters .

contamination with atmospheric moisture occurs. bad repeatability 76 .Use titrant with 2 or 1 mg/mL Oven: .Reduce the value for rel.12 g in 40 mL.Replace solvent . 0.Extend tmin (minimum titration time) Incomplete sample addition . which dissolves the sample. 15 – 20 minutes . The concentration determination is correct only if the di-sodium tartrate has completely dissolved. Poor sample preparation and addition . For samples with low water content < 400 ppm .Change solvent or use fresh solvent after every sample.Samples of low water content (<1000 ppm) are always hygroscopic. Oven: . Sample not dissolved . Water as standard requires practice The use of water for the concentration determination requires experience to obtain repeatable and accurate results.Use higher oven temperature .METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon .Reduce sample size Single values too high Control parameters too fast (= slight overtitration) .Add chloroform or other solvent to methanol. Di-sodium tartrate has only limited solubility In methanol max.Change solvent. . No more sulfur dioxide in the solvent .Sample is oxidized: use nitrogen as a purge gas The results in a series are continuously decreasing Very slow titration with twocomponent titrant Wrong or greatly fluctuating values in the concentration determination with water Dissolving capacity of the solvent is exhausted .Replace the solvent frequently.55 % at 220 °C.Sample is not thermally stable: Use lower oven temperature . If the sample preparation and addition is done carefully.Extend vaporization time (increase t max) .Check drift and blank value .Reduce dVmax and dVmax factor.4 g Increasing value in the concentration determination with di-sodium tartrate Checking drying oven Out of limits.Use back weighing. Determination of the concentration using di-sodium tartrate or Water Standard 10.Increase sample size up to 0. drift stop . With water Standard KF Oven 5.0 is a simpler and a more dependable method.

1.V3 C20 di-Nitrobenzene.V5 C20 Ethers Linear and cyclic V2.V8 C20 V10.: benzamide. C0 Peroxides V2. V3. oxalic acid Oxidizable with iodine: ascorbic acid V2. cresol. diphenylmethanol Weakly basic pKa >8: Imidazole.1 Organic Chemicals Substance Acetals Aldehydes Mono-/polyalcohols Amines Examples R1-CH-(OR2)2 Chlorobenzaldehyde. V5 C20 V2. e. toluidine Oxidizable with iodine: aminophenol Method V2.pyren e. V3.V5 C20. indole. naphthalene > C20 Tar.C22 V16 C0 V10 C0 Nitrocompounds V3. salicylic acid High pKa value: 2-chlorophenol. C0 V2 C20 V15 Low pKa value: phenol.V7 V2. V3.V3.V3.C22 V2. nitrochlorobenzene Dialkylperoxide R-OO-R Alkylperoxide R-OOH Diacyl peroxide V0. o-cresol Side reaction: naphthol.V4. V4 C20 V15 C20 V0. nitrobenzaldehyde > C12 Stearyl alcohol. anthracene. bitumen V4. V4 C20 V2. C0 Sulfur compounds Phenols V0. carbazole Strongly basic: aminopyridine Reaction with methanol: naphthylamine. R-Br.1 Solid samples 11. C20 V11 C0 V2.V4. aminophenol Aromatic/aliphatic sulfonic acids sulfides R-S-R´ disulfides R-SS-R´ thiocyanates R-SCN V0.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11 Karl Fischer Titration: The Method at a Glance 11.V4.V5 C20. V4 C20 Mercaptans V0. R-I R-NCO Benzophenone Method V2. stearamide Weakly acidic: benzoic acid Strongly acidic: malonic acid.V3. anisidine. C0 Esters Carboxylic acid ester R-COOR´ Carbonic anhydride ROCOOR´ 77 . nitrotoluene. C24 Hydrocarbons > C12 Biphenyl.V4 C20 Carbamates Carboxylic acid amides Mono-/polycarboxylic acids RO-CONH2 R-CONR´. V4 V2.g.V4. C0 V2. V4 C20 V2 C20 Substance Halogenated hydrocarbons Isocyanates Ketones Examples R-Cl.

NH4NO3 Nitrites NaNO2 11. C34 V2. KJ.2 Inorganic chemicals Substance Arsenic compounds Bicarbonates carbonates Boron compounds Hydroxides. 78 . glue stick Rubber cement Textile auxiliaries Surfactants powder optical brightener Plastics Polymers Polyethylene. Silicon dioxide Silanols R3Si(OH) Na2SO4. e. NaHCO3 Na2CO3 B2O3 . V32 C20. poly-amides. herbicides Soluble: wool dyes. etc.C40 V2 Adhesives All-purpose glue. disinfectants Salves. V5 V12 V2 V40. multipurpose grease V2 V2.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. V32 C21. C32 Pharmaceuticals Antibiotics. C34 V31 C33 V2. C34 V2. creams Suppositories Tablets Lyophilized preparations V2 V4. V32 C20. indicator dyes. MgCl2 Cu(I) salts: CuCl2 NaH2PO4 .: Na3PO4 Silicon oxide. lotion Lipstick Soaps Toothpaste V4. Na2HPO4 tert. ZnSO4 V2. V31 C32 V2. C34 V10 Na2HAsO3 . NaSO3 Na2S2O5 SnCl2 Nitrates NaNO3 . V31 C20.1. V31 C20. oxides Halogenides Examples Method V30 C30 V34 C32 V31 C32 V21. V30 Insecticides. HBO3 . polyurethane. etc. ski wax Tar. KOH MgO. V31 C31. dispersion dyes Waxes. C32 V15. V31 C20. Phosphate. V8 Cosmetics Creams. CaCl2 . polypropylene. NaAsO2 KHCO3 .3 Technical products – organic Substance Agrochemicals Dyes Examples Method V2 Substance Petrochemicals Examples Method V12 C0 V7 V5. V32 C21. C32 V31 C32 Thiosulfates Tin(II)salts Na2S2O3. polystyrene. C32 V31 C32 Sulfates Silicon compounds Substance Phosphates Examples Method V2. CaO NaCl. paraffins: shoepolish.1.g. V5 V5 V2 V20 V2 V5 V30. fungicides. bitumen lubricating grease. PVC. H3BO3 NaOH. Insoluble: pigments.

almond paste Instant ice tea. jelly Sugar: adherent moisture Chocolate Spices Pepper. C30 V2 V20 Paper. noodles. curry. gummi bears. hardened fat V4. pudding powder. cement Adherent moisture Zeolites Laundry detergent with brightener (hydroxides. mixed spice Mustard Adherent moisture: plain salt. jam Honey.1.5 Technical natural products Substance Cellulose products Fibrous materials Examples Method V30.1. ice cream Dried albumen Powdered milk V2 V13 V2. (V5) V6 C23 V32 C34 V8 V2 V6 V5 79 . perborates) without brightener Total water V30 V2 11. instant coffee. coffee beans.4 Technical products . rye. sea salt V23 V24. noodles. V21 Mortar. tobacco. meat spread.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.inorganic Substance Building materials Fertilizers Examples Method V32 (C34) V6 Substance Minerals Detergents Examples Method V32 V30.1. mayonnaise Shortening. dried vegetables and fruits Hazelnuts. V5 V5 Sugar and sugar products V13 V13 Sugar: total water cont. (V25) V22. plaster. V23 Vegetable products V22. tea.. jellied fruits. (V30) Cheese. broth Biscuits. sea salt Total water: plain salt.almonds instant coffee Fats Butter. V23 Cacao. wood Cellulose powder Wool.6 Food Substance Protein products Examples Method V23 Substance Grains and starchy foods Examples Method V13. candy. V23 V30. Zwieback. corn. Zwieback Yogurt. potato chips Potato flakes Dough. margerine. caramel. silk 11. wheat.

1 Organic and inorganic chemicals Substance Acetals Examples Method V1 C1 Substance Hydrocarbons Examples Method V1 C1 Acetal. toluene. benzyl alcohol Weakly basic: N-methyl aniline heterocyclic amines pyridine.2 Liquid samples 11. HCl Nitrobenzene. disulfides sulfonic acids Mercaptans V1. chinoline Strongly basic: alihatic amines N-butylamine. isobutane. toluidine. crude oil. C1 Sulfurcompounds V1 C1 V0. paraffin Aldehyde Acetaldehyde. t-butyl chloride. petroleum. diamine Easily oxidized with iodine: hydrazine.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. xylene C7 to C14 gasoline.2. chlorotoluene Acetone. hydroxylamine V1 C1 V1 C1 Mineral acids V5 C30 V15 C0 Amines H2SO4. dodecane > C14 heavy oil. hexylamine Reaction with methanol: aniline. chlorobenzene. dioxane. methylethylketone Ketones V10 C10 80 . anisole Methyl benzoate. acetic acid > C2 propionic acid. ethyl acetate Methyl chloride. nitrochlorobenzene Acetonitrile V16 C0 Nitrocompounds V1 C1 V10 C0 Nitriles V1 C1 V0 C0 Peroxides H2O2 V15 Carboxylic acids C1 to C2 formic acid. HNO3. methylal C1 to C7 hexane. ethylal. acrylic acid V15 C0 V1 C1 V1 C1 V1 C1 V1 C1 Acid amides Dimethylformamide Sulfides. nitrotoluene. hexanol. benzaldehyde V11 C0 saturated and unsaturated V4 C1 Alcohols Propanol. cyclohexene. benzene. cyclohexane. pentane. acetophenone. C0 Ethers Esters Halogenated hydrocarbons Dimethylether.

condensed milk Tensides and detergents Agrochemicals (sprays): herbicides. sample input and titration methods. silicon oil Motor oils V5 C1 V30 C30 For more details on the sample preparation. fungicides Acrylic enamels Emulsions in solvents V1 V1 V29 V4 C1 V7 V4 C1 V4 C1 Agrochemicals (sprays): insecticides Synthetic enamels Foods: salad oil. sunflower oil Pharmaceuticals and cosmetics: ethereal oils. massage oil Vegetable oils Technical oils Hydraulic oil.2 Foods and technical products Substance Aqueous solutions Examples Foods: spiced sauce: soy sauce beverages: beer.2. brake fluid. refer to chapter 11.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. 81 . shampoo Method V1 V1 V1 V1 V4 Tensides and detergents Aqueous emulsions Milk products: milk. wine. tinctures Cosmetics: perfume. transformer oil. cream.3. liquor Pharmaceuticals: extrakts.

dProcedure V1 Direct titration Titrant: Solvent: Stir time: Direct titration Titrant: Solvent: Stir time: two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 10 s two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 60 .120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / chloroform 1:5 Stir time: 60 .120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: KF solvent / chloroform 1:1 to 1:2 Stir time: 60 .3. reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Stir time: 30 – 60 s Direct titration methanol free Titrant: two comp.120 s Direct titration with added formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 5 .120 s Delay time: 7 seconds. Direct titration with added toluene Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / toluene 1:1 Stir time: 60 .10 minutes V4 V5 V6 V7 V8 V10 V11 V12 82 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.120 s Direct titration with added 1-decanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / 1-decanol 1:1 Stir time: 60 . These can be also performed using the one-component reagent.3 Titration Methods 11. In this case methanol is used as a solvent. reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Start immediately (autostart) Direct titration with heat (at 50°C) Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent Stir time: 5 .1 Volumetric methods The methods have been developed using 2-component reagents.120 s V2 V3 Direct titration with added 2-propanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / propanol 1:1 Stir time: 60 .10 minutes Direct titration methanol free Titrant: two comp.

15 minutes Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 20 mL buffer or 7g imidazole Stir time: 60 . 50°C Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 10 .150°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .METTLER TOLEDO Good Titration PracticeTM in KF Titration V13 Direct titration with added formamide and heat.20 min With drying oven at 300°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 . Titrant: two component reagent 2 mg H2O/mL Solvent: 50 mL KF solvent Side reaction: KF titration not possible V15 V16 V20 V21 V22 V23 V24 V25 V29 V30 V31 V32 V40 V0 83 .220°C Titrant: two component reagent 5 or 2mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .20 min With drying oven at 160 .120 s Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 5 g benzoic acid Stir time: 1-2 minutes External extraction with methanol at room temperature Titrant: two component reagent 5 mgH2O/mL Solvent: 30 mL KF solvent External extraction with methanol at room temperature in sonicator Remove aliquots of extraction solution over membrane filter with syringe.20 min Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated solvent and inject entire solution into titration cell and titrate. Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with methanol at 50 °C Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide 1:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide/methanol 8:2:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 With drying oven at 110 .

3.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.2 Coulometric methods Method C1 Procedure Direct titration Anolyte: Catholyte: 100 mL anode reagent 5 mL cathode reagent C5 Direct titration with added chloroform Anolyte: 70 mL anode reagent and 30 mL chloroform Catholyte: 5 mL cathode reagent Direct titration methanol free Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones External extraction with methanol or external dissolution in methanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with Methanol in sonicator Remove aliquots of extraction solution over membrane filter with syringe. Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with 1-decanol or external dissolution in 1-decanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with chloroform or external dissolution in chloroform Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction or external dissolution in chloroform (methanol free) Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones With drying oven at 110-130°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 140-150°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 160-190°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 200-250°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 300°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated anolyte and inject entire solution into titration cell and titrate. Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Coulometric determination not possible C10 C20 C21 C22 C23 C24 C30 C31 C32 C33 C34 C40 C0 84 .

paper. almond paste. chocolate Method S1 S1.1 Solids: Characteristics Property Very hard Hard. Pulverize with mortar. In external extraction solvent (methanol.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. tea. silk Cheese. rocks e. bitumen Method S7. gummi bears. 60° C. meat grinder. formamide).) S8 S9 S10 syringe with needle Ø 0. meat Jellied fruits. Dissolve sample or extract water. Inject into titration cell.g.8 mm S11 S12 syringe without needle (Fill very thick samples in back of syringe) weighing boat 85 . Use grate to reduce size. shoepolish Creams. Pulverize with mixer. coffee. 1-decanol. 1-decanol. broth Hardened fat. SiO2 Salts.: CaCO3 . yogurt Salts. greasy Soft. napthalene. wool. ice cream. Melt sample.4. S3 S10. resinous Waxes Examples Butter. Stir. formamide). Cut in small pieces with scissors or knife. cristalline products Wheat. Let solids settle and remove aliquot of remaining solution with syringe. S10 S11 S4. S2 S1. brittle Hard natural products Fibrous natural products Tenacious products Soft products Hard. Use syringe with needle Ø 1. honey. S3 S2. for very thick pastes drill hole in bottom of syringe. creams gel. S11 S4. active ingredients Na-tartrate S9 S12 11. pastes Pulverized soluble Salves. pepper. jelly. S11 S6. or up to approx.4.5 mm or without needle. greasy Examples Minerals. almonds. Zwieback Dried vegetables and fruits. the moisture will be pressed out with pre-heated syringe (with needle Ø 0. S5 S10 S8 Paraffins. At room temp. tobacco.) Homogenize sample well. After sample removal keep sample sealed. S10 S11 S10. noodles.g.4 Sample preparation and input 11. cooled analysis mill. No further preparation necessary.2 Solids: Sample input Method S1 S2 S3 S4 S5 S6 S7 Sample input finely ground sample with weighing boat finely ground sample with weighing boat finely ground sample with weighing boat with spatula with spatula or weighing boat with spatula or weighing boat with spatula Do not use syringe. S8 S10 Property Soft. Homogenize sample well.8 mm ) Fill in backend of syringe Procedure Grind in sealed. potato flakes Tar. (Select stir time so that sample dissolves completely. shake or sonicate. Press through small holes e. margarine Phenols. (Pre-heat syringe with hair dryer or in drying oven. After sample removal keep sample sealed. Break and disperse with high-speed mixer (up to 24000 cpm) in external extraction solvent (methanol. brittle Soft. S10 S2.

0°C in ice bath. average moisture content High moisture content Inhomogeneous (> 50%) (< 1000 ppm) 5 .15°C Examples Propanol.Keep sample in a septum flask.5 mm) Injection with syringe after cooling sample (with needle Ø 0.4. petroleum.8 mm). Hygroscopic sample or low moisture content (< 1000 ppm) . after-shave Beverages.4 Liquids: Sample input Method L1 Sample input Injection with syringe (with needle Ø 0.Rinse syringe with sample 2-3 times (pull up and discard) and condition for 5 minutes. Turbid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. acetone. toluene. glass Visco-Spoon™ 1 mL ME-71492 1.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.2 mm ME-71483 ME-23951 ME-51107668 10 mL 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. aqueous emulsions Acrylic enamels. crude oil. synthetic enamels.8 mm) to remove fresh sample from sample flask and inject this into titration cell through septum or needle hole of three-hole adapter. 11. milk.Homogenize thoroughly by shaking or stirring prior to sample removal. acetone. Boiling point 5 . L2 L3 L4 L5 Injection with syringe L6 Injection with syringe after sample homogenization (with needle Ø 0. H2SO4. .8 mm ME-71482 ME-71484 Septum NS24 ME-23950 Three-hole adapter ME-23982 86 .Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.8 mm) Inhomogeneous emulsions .8 mm) Injection with syringe Procedure Fluid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.4. salad oil Perfume. For each titration use 1 mL syringe (with needle Ø 0. . . acetic acid Silicon oil. glycerine Hexane. glycerine Acetaldehyde Methanol. gasoline. cream Method L1 L2 L3 L4 L4 L1 L5 L6 11.5 Accessories for sample input Syringe Injection needle Weighing boat.8 mm) Injection with syringe (without or with needle Ø 1.4.The pressure loss during sample removal must be compensated with dried air. . . detergents. Samples with high moisture content (> 50%) Rinse syringe with sample 2-3 times.3 Liquids: Characteristics Property Liquid Turbid Low boiling point Hygroscopic Low moisture content Non-hygroscopic.15 °C .Inject sample into titration cell through septum or needle hole of three-hole adapter with 10 mL syringe (with needle Ø 0.Remove sample immediately.Cool sample to approx. .

2412 (1939). R. C. A.J. “Nebenreaktionen in Karl-Fischer-Reagenzien ”. „Mechanism and reaction rate of the Karl Fischer titration reaction. Anal. F... Chem. G. Part IV. 306.C. 15 (4). Rotating ring disk electrode meassurement . “Stöchiometrie und Kinetik der Karl-Fischer –Reaktion in Methanol als Reaktionsmedium”. S. Th. Chem. J. “Mechanism and reaction rate of the Karl Fischer titration reaction. “Determination of Water by Titration with Coulometrically Generated Karl Fischer Reagents”. K. [10] GRÜNKE. “Mechanism and reaction rate of the Karl Fischer titration reaction... 309. BARENDRECHT. 93. Anal. Anal. [3] [4] [5] [6] [7] 87 . E.. 215 – 219 (1959). WÜNSCH. BARENDRECHT. 395-403 (1977). WÜNSCH. Fresenius Z.C. W. 86. Anal.. Chem. Chem. 75-80 (1978). Fresenius J. Verlag Chemie Weinheim (1954) / (in German). SEUBERT A. 71..396 (1981). MEYER. COFINO. E. Fres. 30-32 (1981). [8] SCHOLZ. „Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern“. „Karl-Fischer Reagentien ohne Pyridin. Fresenius Z. Thesis University of Hannover. 16-21 (1989) (in German). Fresenius Z. W. J. „Karl-Fischer Reagentien ohne Pyridin. G. Chem. Ind. J. VERHOFF. J.. Chem.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. Fresenius Z. 94.W. 86. „Wasserbestimmung mit Karl-Fischer-Lösung“.. Z. Part V. SCHOLZ. Chem. D. WERNIMONT.... “Karl-Fischer Reagentien ohne Pyridin“.. VERHOFF. VERHOFF.S. Anal. SMITH. E. Rotating ring disk electrode meassurement“.. 309. A. BRYANT. GRÜNKE. 1999 (in German). [9] WÜNSCH.. G.. 305-315 (1976). E. Anal. „Kinetics and stoichiometry in the Karl Fischer solution“. “Untersuchungen zur Karl-Fischer-Reaktion”. Anal.207 (1980).. First and second order catalytic currents at a rotating disk electrode“. Nature of the Reagent”..4. Chem 368. Soc. Chem. Electroanal. W. J.6 References [1] [2] FISCHER.. “Mechanism and reaction rate of the Karl Fischer titration reaction.396 (1935). Fres. Anal. Potentiometric measurements”. 407-415 (1978). 256-260 (1989) (in German). See literature references in: EBERIUS. 61. 2407 . MITCHELL jr. Ed. Analytical implications”. 139-147 (2000). “Analytical Procedures Employing Karl Fischer Reagent I. 31 (2). Chem. M. Amer.. 123-125 (1981). 705-717 (1976). J.. „Karl-Fischer Reagentien ohne Pyridin. 75.. Both publications from: SEUBERT. SCHOLZ. „The Dead-Stop End Point – As Applied to the Karl Fischer Method for Determining Moisture“. E. Chim. Anal.. BUNSEN. 334. G. VERHOFF. SEUBERT A. 394 . „Karl-Fischer Reagentien ohne Pyridin Genauigkeit der Wasserbestimmung“. E. Acta. Electroanal.. .. 272 – 274 (1943).M. 394 . E. Liebigs Ann. 265 (1853). J. E. SCHOLZ. BARENDRECHT. Einkomponenten Reagentien“. Part II. Angew. J. J. Chem. “Mechanism and reaction rate of the Karl Fischer titration reaction. J. Anal.. Chem. Auflage. Z. Chem. Neue Eichsubstanzen“. J. VERHOFF. Electroanal. Chem. Part I. 303.C. 1. 48. Chem. M. Eng. Zweikomponenten Reagentien mit Imidazol“.C. Fresenius Z. 334. SCHOLZ.. HOPFKINSON. Part III. P. 460-464 (1982). “Reaktionsmechanismen in der Karl-Fischer-Lösung“. Chem. Chem. Anal. 1988 (in German). 203 . Diploma-Thesis at the University of Hannover / Germany. 312.C. S.comparison with the aqueous system“. Electroanal. KOK. E. BOYD. PhD.

Theorie und Praxis“.5 Additional literature HYDRANAL®-Manual.A. 1989 (German) 88 . „Eugen Scholz Reagents for Karl FischerTitration“. Diploma-Thesis at the University of Hannover / Germany. K. „Wasserbestimmung durch Karl-Fischer-Titration . E. WIELAND.. Springer Verlag Berlin. „Untersuchungen einer Karl-Fischer-Reaktion“..METTLER TOLEDO Good Titration PracticeTM in KF Titration [11] LANZ. SCHOLZ. Food Chemistry 96. G. DE AGOSTINI A. 1984. Sigma-Aldrich Laborchemikalien GmbH. "Coulometric Karl Fischer titration with a diaphragm-free cell: Cell design and applications". „Karl Fischer Titration“.. DE CARO C. D. 11. 431-435 (2006). Darmstadt / Germany. RÜEGG K. 1985. SCHÖFFSKI... 2006. GIT Verlag GmbH.. M..30918 Seelze / Germany.

Water amount after extraction = Water amount before extraction WTOT•(mL + (mP•WP) ) = WP•mP + WL•mL where Water content in the sample P (% or ppm).METTLER TOLEDO Good Titration PracticeTM in KF Titration 12 Appendix 12. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent C ⋅ msol + C ⋅ mext ⋅ R = R ⋅ mext + B ⋅ msol C ⋅ mext ⋅ R − R ⋅ mext = B ⋅ msol − C ⋅ msol R ⋅ (C ⋅ mext − mext ) = B ⋅ msol − C ⋅ msol R= 1 ⋅ (B ⋅ msol − C ⋅ msol ) (mext ⋅ (C − 1)) R= R= 1 ⋅ (C ⋅ msol − B ⋅ msol ) (mext ⋅ (1 − C )) since 1 1 =− 1− C C −1 1 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 1 − C ⎝ mext R (%) = 100 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 100 − C ⎝ mext since 1 = 100%. The sample P used for the extraction is not dissolved. WP: This is what we get from the calculation in the KF method. WTOT : Water content of the supernatant extraction solvent (% or ppm) WL : mL : mP : Thus: 1) 2) 3) 4) 5) 6) 7) For % : C ⋅ [msol + (mext ⋅ R )] = R ⋅ mext + B ⋅ msol R C B msol mext Blank value (water content of the solvent. For ppm : R (ppm ) = 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 10 6 − C ⎝ mext since 1 = 106 ppm. % or ppm).1 Formula for the external extraction Principle: • • The water amount (in grams) after extraction is equal to the water amount before extraction. 89 .

00 mg/g (1000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5. the total volume is increased. Total water content (sample + solvent).METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. in % or ppm. Thus. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ 12. 90 .1% SIGMA-ALDRICH HYDRANAL®-Water Standard 0. Water amount after dissolution = Water amount before before dissolution WTOT•(mL + mP) = WP•mP + WL•mL where WP: WTOT : WL : mL : mP : Thus: 1) 2) 3) 4) C ⋅ [msol + mext ] = R ⋅ mext + B ⋅ msol Water content in the sample P (% or ppm) This is what we get from the calculation in the KF method.1 mg/g (100 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 1.01% VWR/VWR/MERCK APURA water standard 0.3 Standards for Karl Fischer coulometry a) For direct measurements: VWR/VWR/MERCK APURA water standard 0.55% (potassium citrate monohydrate) The water content is declared on a test certificate supplied with every vial.2 Formula for the external dissolution Principle: The water amount (in grams) determined by titration is the sum of the water amounts present in the solvent and in the sample. Blank value (water content in% or ppm) of the solvent. The sample P used for the external dissolution is completely dissolved into the solvent. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent R C B msol mext C ⋅ msol + C ⋅ mext = R ⋅ mext + B ⋅ msol R ⋅ mext = C ⋅ msol + C ⋅ mext − B ⋅ msol ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R = C ⋅⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % and ppm: ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%.

chlorinated hydrocarbons (up to C10). edible oils. the sample must completely dissolve in the anolyte.1 For samples that are soluble in methanol or ethanol These include: hydrocarbons (up to C10). esters. ethers. etc.4. ointments. part of the water content is not measured. i. This is limited to a maximum of 30% to prevent the conductivity from falling too low. 30% hexanol APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% hexanol catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit For cells without diaphragm: 91 . more solvent can be added to the anolyte. alcohols. hydrocarbons (C10 to C20). nitrocompounds. an emulsion is formed. the anolyte must be immediately replaced. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG-H (SIGMA-ALDRICH) contains approx.2 For samples that are poorely soluble in methanol or ethanol These include: etherial oils. If the sample does not completely dissolve. 12. Alternatively.4 Reagents and solvents for coulometric analysis To determine its total water content.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Ethanol-based reagents: anolyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) Methanol-based reagents: electrolyte:HYDRANAL® Coulomat AD (SIGMA-ALDRICH) - For cells without diaphragm: - APURA combiCoulomat fritless (VWR/VWR/MERCK) 12.4. This means that if an emulsion is formed in the anolyte. Octanol or hexanol can be added to the anolyte to improve the solubility of these samples. the water content determined is lower than the actual water content of the sample. A number of different anolytes are available to dissolve the various types of samples encountered in practice. etc. acetamide.e. In this case.

the entire titration cell must be thoroughly cleaned because even traces of methanol may cause serious interferences.3 For samples that are insoluble in methanol or ethanol These include: petroleum oils.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 20% hexanol APURA CombiCoulomat fritless (VWR/VWR/MERCK) + 20% hexanol 12. etc. For cells without diaphragm: - Notes on ketones: - - 92 . we recommend the use of a second titration cell. transformer oils. For cells with diaphragm: Methanol-free reagents: anolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat CG-K (SIGMA-ALDRICH) Methanol-free reagents: electrolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) When changing from normal KF anolytes to ketone reagents. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → (CH3)2CO + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O Special methanol-free reagents must be used for these substances. If you measure ketones regularly. hydrocarbons (above C20). For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat A (SIGMA-ALDRICH) + 20% chloroform HYDRANAL® Coulomat AG (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% chloroform catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat fritless (VWR/VWR/MERCK) + 30% chloroform For cells without diaphragm: - 12. silicone oils. Chloroform must be added to the anolyte to ensure the solubility of these samples. This is limited to a maximum of 30% in order to prevent the conductivity from becoming too low.4.4.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal or an acetal and water.

easily be measured with volumetric KF determination. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte.5 mL.2 mL to 0. The use of imidazole increases the pH value in the anolyte.2). - - Notes on aldehydes: - - 12. however. Use the HYDRANAL® buffer (SIGMA-ALDRICH). - For acidic samples. the substances can. 90 mL of anolyte and 5 g salicylic acid or benzoic acid. take an aliquot of anolyte from the titration cell. Coulometric KF titration cannot be used to determine these compounds. e. After a longer standby period. The measurement should not be performed in the titration cell because the electrode introduces too much water. with reactive ketones such as cyclohexanone use only 0. i. The larger the sample.g. acetic acid. With Karl Fischer titrations of acidic and basic samples.: - For basic samples. it is possible that the anolyte is exhausted after a few days even though no further titrations have been performed. the more important the effect of side reactions becomes. amines: - 93 . acetaldehyde) are oxidized at the anode with the formation of water. formic acid. benzaldehyde) can also be determined by coulometric KF titration. 80 mL of anolyte and 20 mL HYDRANAL® buffer.g. Fill the anode compartment with approx. In these cases the pH value of the anolyte should be measured.4.e. It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes. the drift is higher because of the very slow side reaction. the pH value of the anolyte must be adjusted to the range 5. e. 1 mL).5 to 7 (see Section 1. Short chain aldehydes (e. It is important to note that alcohols that react with ketones should not be titrated in this reagent. Fill the anode compartment with approx. Measure the pH with a glass electrode adjusted with aqueous buffers.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift. The special reagent for ketones can also be used for other samples. To do this. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value). Choose relatively small samples (approx. etc. Basic samples must be neutralized with salicylic acid or benzoic acid. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult.g.g. Aromatic aldehydes (e.METTLER TOLEDO Good Titration PracticeTM in KF Titration - If you have titrated a number of ketone samples.

A number of different anolytes are available to dissolve the various types of samples encountered in practice.5 Water Standards for Karl Fischer volumetric titration a) For direct measurements: VWR/VWR/VWR/MERCK APURA® water standard 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. In this case.6. etc.2 For samples poorly soluble in methanol or ethanol These include: etherial oils. chlorinated hydrocarbons (to C10). acetamide. ethers. an emulsion is formed. If it does not completely dissolve. part of the water content is not measured.0 mg/g (1000 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 10. more solvent can be added to the anolyte 12. nitrocompounds. esters. The water content is declared on a test certificate supplied with every vial. hydrocarbons (C10 to C20). One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: Dry methanol Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent Ethanol-based: Titrant: HYDRANAL® Titrant E Solvent: HYDRANAL® Solvent E (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: (SIGMA-ALDRICH) (VWR/Merck) - (SIGMA-ALDRICH) (SIGMA-ALDRICH) 12. edible oils.6 Titrants and solvents for volumetric analysis The sample must be completely dissolved in the anolyte to determine the total water content. This is limited to a maximum of 50%.1 For samples soluble in methanol or ethanol These include: hydrocarbons (to C10).6.55% (potassium citrate monohydrate). Octanol or hexanol can be added to the anolyte to improve the solubility of these samples. alcohols. ointments.1% VWR/VWR/MERCK APURA® water standard 1% SIGMA-ALDRICH HYDRANAL®-Water Standard 1. the result determined is lower than the actual water content. the anolyte must be immediately replaced. etc. Alternatively. In this case. 12.e.0 mg/g (10’000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5. One-component reagents: 94 . i.

Acetal formation: Ketal formation: CH3COH + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O (CH3)2CO + 2 CH3OH → Special methanol-free reagents must be used for these substances. One-component reagents: 95 . This is limited to a maximum of 50% in order to prevent the conductivity from becoming too low.3 For samples insoluble in methanol or ethanol These include: petroleum oils. silicone oils. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® Solver (Crude) apura® CombiSolvent Fats Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM.6. hydrocarbons (above C20).4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® LipoSolver CM.6. Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (VWR/Merck) Two-component reagents: - (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12. MH apura® CombiSolvent Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM. with the formation of water. Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12. or an acetal. transformer oils. etc. Chloroform must be added to the anolyte to ensure the solubility of these samples.

Aromatic aldehydes (e.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-free: Titrant: Solvent: HYDRANAL® Composite 5 K apura® CombiTitrant 5 Keto (SIGMA-ALDRICH) (VWR/Merck) HYDRANAL® Medium K (SIGMA-ALDRICH) HYDRANAL® Working Medium K HYDRANAL® KetoSolver apura® CombiSolvent Keto (VWR/Merck) Notes on ketones: When changing to ketone reagents. with reactive ketones such as cyclohexanone use only 0. e. The use of imidazole leads to a high pH value in the anolyte. amines: 96 . e. - Notes on aldehydes: - - 12. The measurement should not be performed in the titration cell because the electrode introduces too much water. The larger the sample. Measure the pH with a glass electrode adjusted with aqueous buffers. If you have titrated a number of ketone samples. we recommend the use of a second titration cell.g. the drift is higher because of the very slow side reaction. In these cases the pH value of the anolyte should be measured.2). however. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. easily be measured with volumetric KF determination. Fill the anode compartment with approx. the pH value of the anolyte must be adjusted to the range 5.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift. With Karl Fischer titrations of acidic and basic samples. the substances can. Use the HYDRANAL® buffer (SIGMA-ALDRICH). benzaldehyde) can also be determined by coulometric KF titration. 1 mL).g. take an aliquot of anolyte from the titration cell. It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes. It is important to note that alcohols that react with ketones should not be titrated in this reagent. To do this. Choose relatively small samples (approx. the more important the effect of side reactions becomes.g. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value).6. If you measure ketones regularly. formic acid. Coulometric KF titration cannot be used to determine these compounds.2 mL to 0.5 to 7 (see Section 1. The special reagent for ketones can also be used for other samples. etc.5 mL. i.g. acetic acid. Short chain aldehydes (e.: - For basic samples. the entire titration cell must be thoroughly cleaned because even traces of methanol can cause serious interference. 80 mL of anolyte and 20 mL HYDRANAL® buffer. acetaldehyde) are oxidized at the anode with the formation of water. - For acidic samples.e.

The KF solvent contains: sulfur dioxide. Irritant when inhaled. Irritant when inhaled.1 ppm. 90 mL of anolyte and 5 g salicylic acid or benzoic acid. xylene or trichloroethaylene).2 Two-component reagent: Composition: iodine and solvent (methanol. tetrachloromethane. 2-methoxyethanol. Ignition temp. 2methoxyethanol or diethyleneglycolmonomethylether). Keep away from open flames or sparks. Health hazard when inhaled. Keep container tightly closed. Disposal: as an organic solvent. swallowed or allowed to contact skin. Keep container tightly closed and far removed from open flames or sparks. poisonous when inhaled or swallowed.: 46 °C MAK value: 5 ppm Flammable. Keep container tightly closed.: does not burn MAK vlaue: 200 ppm 97 methanol: o-xylene: chloroform: . Disposal: as an organic solvent. Fill the anode compartment with approx. 13. swallowed or allowed to contact skin. 13. Irritant when inhaled.: 87 °C Ignition temp. 13.1 One-component reagent Composition: sulfur dioxide. buffer (imidazole). oxidant Ignition temp. Do not let reagent contact skin or eyes. Skin irritant. Poisonous when inhaled or swallowed. buffer (imidazole) and solvent (methanol. Health hazard when inhaled. Do not let reagent contact skin or eyes.4 Safety data for the KF-components and auxiliary solvents: sulfur dioxide: iodine: diethyleneglycolmonomethylether: 2-methoxyethanol: MAK-value: 200 ppm MAK-value: 0. swallowed or allowed to contact skin.: 28 °C MAK value: 100 ppm Flammable. iodine. and solvent (methanol. Disposal: as an organic solvent. Health hazard upon inhalation. Potential teratogen. Ignition temp. Keep away from open flames or sparks. Health hazard when inhaled. 2methoxyethanol or diethyleneglycolmonomethylether). Safety: Highly flammable. 2-methoxyethanol). Safety: flammable to extremely flammable.: 11 °C MAK value: 200 ppm Highly flammable. Safety: flammable to extremely flammable. Do not let reagent contact skin or eyes. buffer (imidazole) and solvent (methanol. chloroform. Ignition temp. sulfur dioxide.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Basic samples must be neutralized with salicylic acid or benzoic acid. 13 Hazards and waste disposal tips 13.3 Reagents for coulometry: Composition: iodine.

Health hazard upon inhalation 98 . Irreversible damage possible.: 6°C MAK value: 20 ppm Extremely flammable.: 95 °C Irritant for skin and eyes. Potential teratogen.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1-decanol: formamide: toluene: Health hazard when inhaled. Ignition temp.: inflammable MAK value: 20 ppm Irritant for skin and eyes. Ignition temp. Ignition temp.

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are two powerful tools which are meant to facilitate your daily water determination analyses and to contribute to reliable results over the whole lifetime of your instrument. The GTP KF brochure and the application brochure 38 containing dedicated applications on samples from various industry segments. It outlines specific aspects in developing and maintaining a good routine operation with METTLER TOLEDO Compact Coulometric and Volumetric KF as well as Excellence titrators.mt. +41-44 806 77 11 Fax +41-44 806 73 50 Subject to technical changes. www. Routine operation including PQ. Analytical Sonnenbergstrasse 74 CH-8606 Schwerzenbach. Switzerland Tel. method validation. evaluation. Evaluation of the appropriate titration system (DQ) i.Good Titration Practice in water determination Good Titration Practice™ (GTP) in general encompasses three important steps: 1. development of SOPs and maintenance of the validated state of the analytical system. This brochure specifically focuses on Good Titration Practice in water determination using coulometric and volumetric Karl Fischer Titration. ©09/2009 Mettler-Toledo AG Printed in Switzerland.e. specification of the analytical requirements and purchase decision 2. ME-51725145A Markt Support AnaChem .com For more information Mettler-Toledo AG. Installation of the selected analytical system comprising IQ and OQ and training of personnel 3.

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